阅读说明：本技术 四齿配体、金(iii)配合物及其制备方法和应用 (Tetradentate ligand, gold (III) complex, and preparation method and application thereof ) 是由 支志明 于 2019-08-23 设计创作，主要内容包括：本发明提供一种具有式(I)结构的四齿配位基金(III)配合物,该配合物作为发光器件中的发光层材料或掺杂剂,得到的发光器件具有高的外量子效率,且效率滚降低；此外,本发明提供的四齿配体的制备工艺简单,收率理想,更关键的是该原料的制备反应可控定,结果重现性好,适于工业化应用。(The invention provides a tetradentate coordination gold (III) complex with a structure shown in a formula (I), which is used as a luminescent layer material or a dopant in a luminescent device, and the obtained luminescent device has high external quantum efficiency and reduced efficiency roll; in addition, the preparation process of the tetradentate ligand provided by the invention is simple, the yield is ideal, more importantly, the preparation reaction of the raw material is controllable, the result reproducibility is good, and the method is suitable for industrial application.)

1. A gold (III) complex, wherein the gold (III) complex has a chemical structure according to formula (I):

wherein the content of the first and second substances,

X¹、X²、X³independently selected from carbon or nitrogen, and X¹、X²、X³And only one of them is nitrogen;

Y¹is O, CR¹⁵R¹⁶Or S;

R¹～R¹⁶independently selected from hydrogen, deuterium, halogen, nitro, cyano, isocyano, trifluoromethyl, or independently selected from substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, heteroaryloxy, NR¹⁷R¹⁸An acyl group, an acylamino group, an acyloxy group, an ester group, an acylamino group, a sulfonamido group, a sulfonyloxy group, a sulfonate ester, a sulfonamide or a trialkylsilyl group; wherein R is¹⁷、R¹⁸Independently selected from the group consisting of substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, or heteroaryloxy;

or, R¹～R¹⁸Any two adjacent or similar groups and the carbon atom in which the two adjacent or similar groups are located form a 5-15-membered ring.

2. The gold (III) complex according to claim 1, wherein R is¹～R¹⁶Independently selected from hydrogen, tritium, halogen, nitro, cyano, isocyano, trifluoromethyl, or independently selected from substituted or unsubstituted: c_1～15Alkyl of (C)_3～18Cycloalkyl of, C_2～15Alkenyl of (C)_3～18Cycloalkenyl group of (A), C_2～15Alkynyl of (A), C_6～30Aryl of (C)_7～35Aralkyl of (2), C_2～20Heteroalkyl of (a), C_3～20Heterocycloalkyl of (A), C_5～30Heterocycloalkenyl of (A), C_5～30Heteroaryl of (A), C_6～30Heteroaralkyl of (2), C_1～20Alkoxy group of (C)_6～30Aryloxy group of (A), C_5～30Heteroaryloxy group of (A), NR¹⁷R¹⁸An acyl group, an acylamino group, an acyloxy group, an ester group, an acylamino group, a sulfonamido group, a sulfonyloxy group, a sulfonate group, a sulfonamido group or a trialkylsilyl group; wherein R is¹⁷、R¹⁸Independently selected from the group consisting of substituted or unsubstituted: c_1～15Alkyl of (C)_3～18Cycloalkyl of, C_2～15Alkenyl of (C)_3～18Cycloalkenyl group of (A), C_2～15Alkynyl of (A), C_6～40Aryl of (C)_7～45Aralkyl of (2), C_2～20Heteroalkyl of (a), C_3～20Heterocycloalkyl of (A), C_5～30Heterocycloalkenyl of (A), C_5～30Heteroaryl of (A), C_6～30Heteroaralkyl of (2), C_1～20Alkoxy group of (C)_6～30Aryloxy group of or C_5～30A heteroaryloxy group of (a);

preferably, the NR is¹⁷R¹⁸Is a group represented by the following structure or a derivative group in which hydrogen on the group represented by the following structure is substituted with one or more, the same or different substituents:

wherein, Y²Is O, S, CR²⁰R²¹、SiR²²R²³Or NR²⁴，R²⁰～R²⁴Independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C_1～15Alkyl, substituted or unsubstituted C_6～30Aryl of (a); the substituent in the substituted derivative group is halogen or C_1～20Alkyl of (C)_1～20Alkoxy group of (C)_1～20Alkylthio, 5-to 6-membered cycloalkyl, 5-to 6-membered heterocycloalkyl, C_6～30Aryl of (C)_6～30Aryloxy group of (A), C_5～30Heteroaryl of (A), C_2～15Alkenyl or C_2～15Alkynyl group of (1).

3. The gold (III) complex according to claim 1, wherein R is¹～R¹⁶The total number of carbon atoms in the group (b) is 1 to 80, preferably 6 to 60, and more preferably 12 to 50.

4. The gold (III) complex according to claim 1, wherein R is¹～R¹⁶At least one of which is not hydrogen;

and/or, R¹～R¹⁴¹⁴At least one of (A) is NR¹⁷R¹⁸；

And/or, R¹～R¹⁴In which 1 to 3 groups are NR¹⁷R¹⁸A group of (a);

and/or, R²、R³、R⁶、R⁹、R¹²、R¹³At least one of (A) is NR¹⁷R¹⁸。

5. The gold (III) complex according to claim 1, wherein R is¹～R¹⁶When the substituent group is a substituent-containing group, the substituent group on the group is halogen, nitro, cyano, trifluoromethyl or C_1～20Alkyl of (C)_1～20Alkoxy group of (C)_1～20Alkylthio, 5-to 6-membered cycloalkyl, 5-to 6-membered heterocycloalkyl, C_6～30Aryl of (C)_6～30Aryloxy group of (A), C_5～30Heteroaryl of (A), C_2～15Alkenyl or C_2～15Alkynyl group of (1).

6. The gold (III) complex according to claim 1, wherein R is¹～R¹⁶Independently selected from the group consisting of hydrogen, tritium, fluorine, chlorine, bromine, iodine, nitro, cyano, isocyano, trifluoromethyl, ester, acyloxy, amide, sulfonamide, sulfonyloxy, sulfonate, sulfonamide, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentyloxy, isopentyloxy, neopentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, vinyl, propenyl, butenyl, pentenyl, hexenyl, ethynyl, propynyl, butynyl, pentynyl, n-ynyl, n-nonyl, n-decyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexyl, and the like, Cyclopentenyl, cyclohexenyl, cycloheptenyl, phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, phenylmethyl, phenylethyl, phenylpropyl, phenoxy, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, tert-butylphenyl, n-pentylphenyl, isopentylphenyl, neopentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, xylylenylPhenyl group, diethylphenyl group, di-n-propylphenyl group, diisopropylphenyl group, di-n-butylphenyl group, diisobutylphenyl group, di-t-butylphenyl group, di-n-pentylphenyl group, diisopentylphenyl group, dineopentylphenyl group, di-n-hexylphenyl group, di-n-heptylphenyl group, di-n-octylphenyl group, di-n-nonylphenyl group, di-n-decylphenyl group, diphenylaminophenyl group, furyl group, pyranyl group, pyridyl group, pyrimidyl group, thiazolyl group, oxazolyl group, imidazolyl group, isoxazolyl group, pyrrolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, thienyl group, furyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, indolyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, bipyridyl group, acridinyl group, phenanthridinyl group, phenanthrolinyl group, quinazolinyl group, benzimidazolyl group, benzofuranyl group, benzothienyl group, benzothiazolyl group, benzisoxazolyl group, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, thiazinyl, or the following structural formula:

7. the gold (III) complex according to claim 1, wherein R is¹～R¹⁸Any two adjacent groups or similar groups and the carbon atoms where the adjacent groups and the groups are located form 5-15 membered aromatic rings, 5-15 membered heterocyclic rings, 5-15 membered naphthenes or 5-15 membered unsaturated naphthenes;

wherein the heteroatoms in the heterocycle are independently selected from nitrogen, sulfur or oxygen.

8. The gold (III) complex according to claim 1, characterized in that the gold (III) complex is in particular as follows:

9. a method for preparing a tetradentate gold (III) complex, comprising: reacting the tridentate coordination gold (III) complex with the structure of the formula (0-II) under the microwave condition to obtain the structure of the formula (0-I);

or: reacting an organic compound with a structure shown in a formula (0-III) with a gold (III) reagent under the microwave condition to obtain a tetradentate coordination gold (III) complex with a structure shown in a formula (0-I);

wherein the content of the first and second substances,

X¹、X²、X³independently selected from carbon or nitrogen, and X¹、X²、X³And only one of them is nitrogen;

X’¹、X’²、X’³independently selected from CH or nitrogen, and X'¹、X’²、X’³And only one of them is nitrogen;

Y¹is O, CR¹⁵R¹⁶Or S;

X_ais F, Cl, Br, I, OTf, OCOCOCF₃、OAc、OH、NTf₂；

R¹⁵、R¹⁶Independently selected from hydrogen, deuterium, halogen, nitro, cyano, isocyano, trifluoromethyl, or independently selected from substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, heteroaryloxy, NR¹⁷R¹⁸An acyl group, an acylamino group, an acyloxy group, an ester group, an acylamino group, a sulfonamido group, a sulfonyloxy group, a sulfonate ester, a sulfonamide or a trialkylsilyl group; wherein R is¹⁷、R¹⁸Independently selected from the group consisting of substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,Aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, or heteroaryloxy;

or, R¹～R¹⁸Any two adjacent or similar groups and the carbon atom in which the two adjacent or similar groups are positioned form a 5-15-membered ring;

A. b, C, D is independently substituted or unsubstituted aromatic ring, substituted or unsubstituted heteroaromatic ring, and when A, B, C, D contains multiple substituents on the ring, any two adjacent or nearby substituents can be linked to form 5-15 rings.

10. A method for preparing a gold (III) complex, comprising:

reacting a tridentate coordination gold (III) complex with a structure shown in a formula (II) under a microwave condition to obtain a complex with a structure shown in a formula (I);

or:

mixing and reacting an organic compound with a structure shown in a formula (III) with a gold (III) reagent under a microwave condition to obtain a tetradentate coordination gold (III) complex with a structure shown in a formula (I);

wherein the content of the first and second substances,

X¹、X²、X³independently selected from carbon or nitrogen, and X¹、X²、X³And only one of them is nitrogen;

X’¹、X’²、X’³independently selected from CH or nitrogen, and X'¹、X’²、X’³And only one of them is nitrogen;

Y¹is O, CR¹⁵R¹⁶Or S;

X_ais F, Cl, Br, I, OTf, OCOCOCF₃OAc, OH or NTf₂；

R¹～R¹⁶Independently selected from hydrogen, deuterium, halogen, nitro, cyano, isocyano, trifluoromethyl, or independently selected fromThe following groups, optionally substituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, heteroaryloxy, NR¹⁷R¹⁸An acyl group, an acylamino group, an acyloxy group, an ester group, an acylamino group, a sulfonamido group, a sulfonyloxy group, a sulfonate ester, a sulfonamide or a trialkylsilyl group; wherein R is¹⁷、R¹⁸Independently selected from the group consisting of substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, or heteroaryloxy;

or, R¹～R¹⁸Any two adjacent or similar groups and the carbon atom in which the two adjacent or similar groups are located form a 5-15-membered ring.

11. The method according to claim 10, wherein the reaction of the organic compound of formula (III) with the gold (III) reagent is specifically:

mixing an organic compound with a structure shown in a formula (III), a gold (III) reagent and a second solvent for reaction under the microwave condition to obtain an intermediate;

wherein the gold (III) reagent is selected from Au (OAc)₃、AuCl₃、Au(OTf)₃、HAuCl₄、KAuCl₄、NaAuCl₄、KAuBr₄Or NaAuBr₄Preferably Au (OAc)₃(ii) a The second solvent is a mixture consisting of one or more of water, a conventional alcohol solvent, acetonitrile, DMF, DMSO, DMA, THF and 1, 4-dioxane;

mixing the intermediate with a first solvent for further reaction to obtain a tetradentate coordination gold (III) complex with a structure shown in a formula (I);

wherein the first solvent is water or a mixture of water and one or more of ACN, DMF, DMA, THF and 1, 4-dioxane.

12. The tetradentate ligand has a structure shown in a formula (III).

Wherein the content of the first and second substances,

X’¹、X’²、X’³independently selected from CH or nitrogen, and X'¹、X’²、X’³And only one of them is nitrogen;

Y¹is O, CR¹⁵R¹⁶Or S;

R¹～R¹⁶independently selected from hydrogen, deuterium, halogen, nitro, cyano, isocyano, trifluoromethyl, or independently selected from substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, heteroaryloxy, NR¹⁷R¹⁸An acyl group, an acylamino group, an acyloxy group, an ester group, an acylamino group, a sulfonamido group, a sulfonyloxy group, a sulfonate ester, a sulfonamide or a trialkylsilyl group; wherein R is¹⁷、R¹⁸Independently selected from the group consisting of substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, or heteroaryloxy;

or, R¹～R¹⁸Any two adjacent or similar groups and the carbon atom in which the two adjacent or similar groups are located form a 5-15-membered ring.

13. Use of a gold (III) complex according to any one of claims 1 to 8 for the preparation of a light-emitting device.

14. A light-emitting device comprising a light-emitting layer containing the gold (III) complex according to any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of luminescent materials, in particular to a tetradentate ligand, a gold (III) complex, and a preparation method and application thereof.

Background

Since the advent of organic and polymer electroluminescent materials and corresponding devices, Organic Light Emitting Diodes (OLEDs), the research trend in academia and industry has been driven by the advantages of light weight, thin profile, fast response speed, low driving voltage, wide viewing angle, suitability for the manufacture of flexible substrates, and the like, and is considered to be the most promising material for the next generation of flat panel display technology in the fields of commercial flat panel displays and solid state light emitting systems.

The luminescent material is the key of the OLED display technology, and the good performance of the luminescent material is mainly reflected in the aspects of high photoluminescence quantum yield (PLQY), high Electroluminescence (EL) efficiency, high External Quantum Efficiency (EQE), short radiation decay life (radiative lifetime), low roll-off efficiency, adjustable color, high luminescent color purity, long device operation life, suitability for the kinescope manufacturing process and the like, and the performance of the luminescent material is mainly dependent on the chemical structure of a metal complex used as the luminescent material.

The metal complex is one of the most widely studied luminescent materials, because the existence of the heavy metal center can increase the spin orbit coupling tendency of the mixed singlet state and triplet state, shorten the luminescent lifetime, thereby effectively reducing the self-quenching and the luminescent saturation of the triplet state caused by long luminescent lifetime, and greatly improving the electro-optic conversion efficiency. Organometallic complexes with Ir (III), Ru (II), Pt (II) as central metals have abundant and excellent light-emitting characteristics, and have been studied intensively at present, and a series of light-emitting materials with excellent performance are developed, such as porphyrin-based Pt (II) triplet emitters PtOEP, cyclometallated Ir (III) emitters [ Ir (ppy)3], [ Ir (4, 6-dFppy)2(pic) ] and the like, which can be used as dopants for manufacturing high-efficiency OLEDs, and are partially commercialized. However, the development of the OLED light-emitting material still has a great limitation at present, because different metal centers and different ligand structures such as spatial configuration, conjugation effect, electrical property, substituent effect, etc. all have very important influence on the light-emitting property of the metal complex, and are often difficult to predict, the available central heavy metals have limited types and high cost, the complex rule of obtaining good luminescence property is difficult to follow due to the diversified ligand structures, thereby leading to high difficulty in finding new luminescent materials, low efficiency, narrow adjustable range of the color of the luminescent materials, still less selectivity of the luminescent materials which can be applied in commercialization, and the like, therefore, based on the design, modification or modification of the micro-chemical structure of the novel organic metal complexes of different heavy metal centers, the method has important significance for the discovery of new luminescent materials with excellent luminescent properties, and can further reduce the manufacturing cost of the display screen.

Au is more abundant and cheaper than metals such as Pt and Ir, but development of Au complexes as light-emitting materials is still under research stage, and the subject group Yam has made many pioneering works in this field [ Nature Photonics, 20 ]19，13，185-191；Angew.Chem.Int.Ed.2018，57，5463-5466；J.Am.Chem.Soc.2017，139，10539-10550；J.Am.Chem.Soc.2014，136，17861-17868；Angew.Chem.Int.Ed.2013，52，446；J.Am.Chem.Soc.2010，132，14273-14278；US8415473；J.Am.Chem.Soc.2007，129，4350；Angew.Chem.Int.Ed.2005，44，3107；Chem.Commun.2005，2906；J.Chem.Soc.，Dalton Trans.1993，1001.]They use the low energy d-d Ligand Field (LF) to lead to the theory of severe self-quenching to explain the problem of low luminescence efficiency of au (III) complexes and enhance luminescence by introducing ligands with strong sigma-donor type, such as dendritic alkynyl ligands or dipolar ligands containing triphenylamine, benzimidazole, etc., into au (III) complexes by design; nature Photonics, 2019, 13, 185-191 have recently reported that a gold (III) complex of a tridentate ligand can be obtained, and 21.6% of EQE and 1000cd m of maximum external quantum efficiency can be obtained after optimization^-2Under the condition of less than 15 percent of efficiency roll-off, besides, the EQE of the complex obtained under the condition of a solution method is less than 13.5 percent, and the current efficiency is less than 37.4cd A^-1Much more, the EQE drops sharply with the increase of the light-emitting brightness

However, related researches only show one example of a report [ US20170222164] that a metal complex based on tetradentate coordination may bring about different luminescent properties or device properties, and a literature introduces a substituted alkynyl group which can provide a strong sigma-donor and has a larger conjugated system or a fused heterocyclic aryl group with two polarities as a coordination point with Au (iii) into a tridentate ligand Au complex in a bridging manner, so that the yield of single-step synthesis is 42-72%, the maximum external quantum efficiency is lower than 11.1% under a solution method and a doping concentration of 20%, and the EQE is sharply reduced along with the increase of current density, and the proposal of the metal complex has better luminescent brightness, but effective proof data is not provided, and the metal complex is difficult to serve as an evaluation basis.

In addition, microwave synthesis for the synthesis of Au (III) complexes is currently practicedThe formation method is only limited to be applied to the two/three-tooth gold (III) complex, but the application of the microwave technology to the synthesis of the four-tooth coordination gold (III) complex with gold-carbon bond is not reported. In 2012, Tilset and co-workers dissolved the ligands 2- (4-methylphenyl) pyridine and gold acetate in a mixed solvent TFA/H₂In O, a bidentate gold (III) complex [ Organometallics 2012, 31, 6567-6571 ] is obtained in a microwave reactor]. In 2018, the tridentate gold (III) complex is obtained by adopting 2- (3, 5-di-tert-butylphenyl) pyridine as a ligand and reacting under the same conditions. Commun, 2018, 54, 11104-]. In 2015, Nevado et al utilized microwave technology to obtain C ^ C ^ N tridentate gold (III) compounds [ Angew.chem.Iht.Ed.2015, 54, 14287-]. In 2017, Venkatesan et al oxidized Au (I) compound into Au (III) complex, and then activated carbon-hydrogen C-H bond on ligand by microwave technique to achieve the purpose of coupling and synthesizing bidentate gold (III) compound [ J.Mater.chem.C, 2017, 5, 3765-]. The synthesis method of the tetradentate ligand is difficult, the synthesis method provided by the existing literature has many steps and long operation period, and experiments prove that the reaction reproducibility is poor, the yield is unstable, the modification space of the complex applicable to the method is narrow, many designed candidate complexes cannot be synthesized by the method, and the method is not beneficial to research and development and commercial preparation, so that the tetradentate ligand Au (III) complex has better stability compared with a tridentate complex, but the development is less and the commercial application prospect is not good.

In summary, although the development and research of the Au complex as the luminescent material in the OLED have been advanced primarily, the Au complex provided by the prior art has few cases meeting the requirements and far cannot meet the requirements of luminescent materials, and most products have still not ideal parameter indexes of various luminescent properties, such as low external quantum efficiency and obvious efficiency roll-off, which is 1000cd a^-1The external quantum efficiency can not meet the requirement under the practical brightness, and has larger gap from commercialization, so that the ligand Au complex with a novel structure and better luminescence property is developed, and particularly, the tetradentate structure with excellent performance and preparation method is obtainedThe ligand Au complex has important significance.

Disclosure of Invention

In view of the above, the present invention aims to provide a tetradentate ligand, a gold (III) complex, and a preparation method and an application thereof, wherein an optical device prepared from the gold (III) complex obtained from the tetradentate ligand provided by the present invention has high external quantum efficiency and reduced efficiency, and the preparation method of the complex is easy and is easy to realize industrial production.

The invention provides a tetradentate coordination gold (III) complex with a structure of formula (I), which comprises a metal center and a cyclometallated tetradentate ligand, wherein the metal center is + 3-valent gold which has four coordination sites in a plane square shape, and the cyclometallated tetradentate ligand is occupied clockwise or anticlockwise in the order of coordination atoms C, C, N, C to form a 5-5-6-membered fused ring structure containing a gold-carbon bond (Au-C) and an N donor bond (Au ← N), namely when two adjacent coordination atoms in the tetradentate ligand are separated by 3 connected covalent bonds (single bond or double bond), the tetradentate ligand and the gold form a five-membered ring in coordination; when two adjacent coordination atoms in the tetradentate ligand are separated by 4 connected covalent bonds (single bond or double bond), the tetradentate ligand is coordinated with gold to form a six-membered ring; experiments show that the coordination atoms are independently positioned on different aromatic rings of the tetradentate ligand, and the complex is used as a material or a dopant of a light-emitting layer in a light-emitting device, so that the prepared light-emitting device has high external quantum efficiency and the efficiency is reduced; the complex of the invention also has thermally induced delayed fluorescence (TADF); in addition, the preparation process of the tetradentate ligand provided by the invention is simple, the yield is ideal, and more importantly, the preparation reaction of the raw material is controllable and stable, the result reproducibility is good, and the method is suitable for industrial application.

Drawings

Fig. 1 is a view showing a structure of a light emitting device according to an embodiment of the present invention;

FIG. 2 shows the solution solubility of (a) complexes 1 and 2 and (b) complexes 5 and 6 in deoxygenated toluene (Au (III) complex at room temperature of 2X 10^-5mol/L) absorption spectrum;

FIG. 3 shows an embodiment of the present inventionIn (a) Complex 3, (b) Complex 4, (c) Complex 7 and (d) Complex 8 in different deoxygenated solvents at room temperature (solution solubility of gold (III) Complex 2X 10)^-5mol/L) absorption spectrum;

FIG. 4 shows that, in one embodiment of the present invention, the solution solubility of (a) complex 1-4 and (b) complex 5-8 in deoxygenated toluene (Au (III) complex is 2X 10 at room temperature^-5mol/L) emission spectra of (c) complex 4 at 2X 10 at room temperature^-5Emission spectra in deoxygenated/oxygenated toluene at mol/L concentration (asterisk "-" indicates 2-step transition at 380nm excitation wavelength);

FIG. 5 shows that, in one embodiment of the present invention, the solution solubility of (a) complex 3, (b) complex 4, (c) complex 7 and (d) complex 8 in different deoxygenated solvents (Au (III) complex is 2X 10 at room temperature^-5mol/L) emission spectrum;

FIG. 6 shows the emission spectra of (a) complexes 1 to 4 and (b) complexes 5 to 8 in a PMMA thin film (the mass fraction of Au (III) complex in the thin film is 4%) at room temperature in an example of the present invention;

FIG. 7 shows that in one embodiment of the present invention, complex 9 has a solution solubility of 2X 10 in deoxygenated dichloromethane (gold (III) complex at room temperature^-5mol/L), an absorption spectrum (a) and an emission spectrum (b), an emission spectrum (c) of the complex 9 in a PMMA thin film (mass fraction of Au (III) complex in the thin film is 4%) at room temperature;

FIG. 8 shows a TGA profile of each complex in an embodiment of the present invention, wherein (a) complex 3 loses 2% weight at 394 deg.C; (b) the weight loss of the complex 4 is 2 percent when the temperature is raised to 429 ℃;

FIG. 9 shows the results of testing the light emitting properties of an OLED device prepared using complex 4 as a dopant in accordance with an embodiment of the present invention: (a) the light emission pattern of the electroluminescent OLED under different doping concentrations of the complex 4; (b) the current density of the complex 4 under different doping concentrations and different voltages; (c) the change curve of the luminous brightness along with the voltage; (d) the change curve of the external quantum efficiency along with the luminous brightness;

FIG. 10 shows the results of testing the light emitting properties of an OLED device prepared using complex 7 as a dopant according to an embodiment of the present invention;

FIG. 11 shows the results of testing the light emitting properties of an OLED device prepared using complex 7 as a dopant according to an embodiment of the present invention;

FIG. 12 shows the results of testing the light emitting properties of OLED devices prepared using complex 8 as a dopant in accordance with one embodiment of the present invention.

Detailed Description

The invention provides a gold (III) complex, which is characterized by having a chemical structure shown as a formula (I):

wherein the content of the first and second substances,

X¹、X²、X³independently selected from carbon or nitrogen, and X¹、X²、X³And only one of them is nitrogen;

Y¹is O, CR¹⁵R¹⁶Or S;

R¹～R¹⁶independently selected from hydrogen, deuterium, halogen, nitro, cyano, isocyano, trifluoromethyl, or independently selected from substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, heteroaryloxy, NR¹⁷R¹⁸An acyl group, an acylamino group, an acyloxy group, an ester group, an acylamino group, a sulfonamido group, a sulfonyloxy group, a sulfonate ester, a sulfonamide or a trialkylsilyl group; wherein R is¹⁷、R¹⁸Independently selected from the group consisting of substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, or heteroaryloxy;

or, R¹～R¹⁸Any two adjacent or similar groups and the carbon atom in which the two adjacent or similar groups are located form a 5-15-membered ring.

In some embodiments, the R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶Independently selected from hydrogen, deuterium, halogen, nitro, cyano, isocyano, trifluoromethyl, or independently selected from substituted or unsubstituted: c_1～15Alkyl of (C)_3～18Cycloalkyl of, C_2～15Alkenyl of (C)_3～18Cycloalkenyl group of (A), C_2～15Alkynyl of (A), C_6～30Aryl of (C)_7～35Aralkyl of (2), C_2～20Heteroalkyl of (a), C_3～20Heterocycloalkyl of (A), C_5～30Heterocycloalkenyl of (A), C_5～30Heteroaryl of (A), C_6～30Heteroaralkyl of (2), C_1～20Alkoxy group of (C)_6～30Aryloxy group of (A), C_5～30Heteroaryloxy group of-NR¹⁷R¹⁸An acyl group, an acylamino group, an acyloxy group, an ester group, an acylamino group, a sulfonamido group, a sulfonyloxy group, a sulfonate group, a sulfonamido group or a trialkylsilyl group; wherein R is¹⁷、R¹⁸Independently selected from the group consisting of substituted or unsubstituted: c_1～15Alkyl of (C)_3～18Cycloalkyl of, C_2～15Alkenyl of (C)_3～18Cycloalkenyl group of (A), C_2～15Alkynyl of (A), C_6～40Aryl of (C)_7～45Aralkyl of (2), C_2～20Heteroalkyl of (a), C_3～20Heterocycloalkyl of (A), C_5～30Heterocycloalkenyl of (A), C_5～30Heteroaryl of (A), C_6～30Heteroaralkyl of (2), C_1～20Alkoxy group of (C)_6～30Aryloxy group of or C_5～30A heteroaryloxy group of (a).

In some embodiments, the R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶Independently selected from hydrogen, deuterium,Halogen, nitro, cyano, isocyano, trifluoromethyl, or independently selected from the group consisting of substituted or unsubstituted: c_3～10Alkyl of (C)_5～12Cycloalkyl of, C_4～10Alkenyl of (C)_5～12Cycloalkenyl group of (A), C_4～10Alkynyl of (A), C_8～15Aryl of (C)_10～20Aralkyl of (2), C_3～10Heteroalkyl of (a), C_5～8Heterocycloalkyl of (A), C_6～15Heterocycloalkenyl of (A), C_8～15Heteroaryl of (A), C_8～15Heteroaralkyl of (2), C_3～10Alkoxy group of (C)_10～20Aryloxy group of (A), C_8～15Heteroaryloxy group of-NR¹⁷R¹⁸An acyl group, an acylamino group, an acyloxy group, an ester group, an acylamino group, a sulfonamido group, a sulfonyloxy group, a sulfonate group, a sulfonamido group or a trialkylsilyl group; wherein R is¹⁷、R¹⁸Independently selected from the group consisting of substituted or unsubstituted: c_1～15Alkyl of (C)_3～18Cycloalkyl of, C_2～15Alkenyl of (C)_3～18Cycloalkenyl group of (A), C_2～15Alkynyl of (A), C_6～40Aryl of (C)_7～45Aralkyl of (2), C_2～20Heteroalkyl of (a), C_3～20Heterocycloalkyl of (A), C_5～30Heterocycloalkenyl of (A), C_5～30Heteroaryl of (A), C_6～30Heteroaralkyl of (2), C_1～20Alkoxy group of (C)_6～30Aryloxy group of or C_5～30A heteroaryloxy group of (a).

In some embodiments, the NR is¹⁷R¹⁸Is a group represented by the following structure or a derivative group in which hydrogen on the group represented by the following structure is substituted with one or more, the same or different substituents:

wherein, Y²Is O, S, CR²⁰R²¹、SiR²²R²³Or NR²⁴，R²⁰～R²⁴Independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C_1～15Alkyl of (2)Substituted or unsubstituted C_6～30Aryl of (a); the substituent in the substituted derivative group is halogen or C_1～20Alkyl of (C)_1～20Alkoxy group of (C)_1～20Alkylthio, 5-to 6-membered cycloalkyl, 5-to 6-membered heterocycloalkyl, C_6～30Aryl of (C)_6～30Aryloxy group of (A), C_5～30Heteroaryl of (A), C_2～15Alkenyl or C_2～15Alkynyl group of (1).

In some embodiments, the R is¹～R²⁴When the substituent group is a substituent-containing group, the substituent group on the group is halogen, nitro, cyano, trifluoromethyl or C_1～20Alkyl of (C)_1～20Alkoxy group of (C)_1～20Alkylthio, 5-to 6-membered cycloalkyl, 5-to 6-membered heterocycloalkyl, C_6～30Aryl of (C)_6～30Aryloxy group of (A), C_5～30Heteroaryl of (A), C_2～15Alkenyl or C_2～15Alkynyl group of (1).

In some embodiments, the R is¹～R²⁴When the group is a substituent-containing group, the substituent on the group is fluorine, chlorine, bromine, iodine, nitro, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, vinyl, propenyl, butenyl, pentenyl, hexenyl, ethynyl, propynyl, butynyl, pentynyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, or the like, Phenylmethyl, phenylethyl, phenylpropyl, phenoxyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, tert-butylphenyl, n-pentylphenyl, isopentylphenyl, neopentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-hexylphenylNonylphenyl group, n-decylphenyl group, dimethylphenyl group, diethylphenyl group, di-n-propylphenyl group, diisopropylphenyl group, di-n-butylphenyl group, diisobutylphenyl group, di-tert-butylphenyl group, di-n-pentylphenyl group, diisopentylphenyl group, dineopentylphenyl group, di-n-hexylphenyl group, di-n-heptylphenyl group, di-n-octylphenyl group, di-n-nonylphenyl group, di-n-decylphenyl group, diphenylaminophenyl group, furyl group, pyranyl group, pyridyl group, pyrimidyl group, thiazolyl group, oxazolyl group, imidazolyl group, isoxazolyl group, pyrrolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, thienyl group, furyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, indolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, bipyridyl group, acridinyl group, phenanthridinyl group, phenanthrolinyl group, quinazolinyl group, benzimidazolyl group, benzofuranyl group, benzoxazolyl, benzisoxazolyl, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, or thiazinyl.

In some embodiments, the R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶Independently selected from the group consisting of hydrogen, deuterium, fluorine, chlorine, bromine, iodine, nitro, cyano, isocyano, trifluoromethyl, ester, acyloxy, amide, sulfonamide, sulfonyloxy, sulfonate, sulfonamide, trimethylsilyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentyloxy, isopentyloxy, neopentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, vinyl, propenyl, butenyl, pentenyl, hexenyl, ethynyl, propynyl, butynyl, pentynyl, n-ynyl, and the like, Cyclopentenyl, cyclohexenyl, cycloheptenyl, phenyl, and the like,Naphthyl, anthryl, phenanthryl, fluorenyl, phenylmethyl, phenylethyl, phenylpropyl, phenoxy, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, tert-butylphenyl, n-pentylphenyl, isopentylphenyl, neopentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, dimethylphenyl, diethylphenyl, di-n-propylphenyl, diisopropylphenyl, di-n-butylphenyl, diisobutylphenyl, di-tert-butylphenyl, di-n-pentylphenyl, diisopentylphenyl, dineopentylphenyl, di-n-hexylphenyl, di-n-heptylphenyl, di-n-octylphenyl, di-n-nonylphenyl, di-n-decylphenyl, diphenylaminophenyl, furyl, pyranyl, pyridyl, pyrimidinyl, thiazolyl, oxazolyl, imidazolyl, etc, Isoxazolyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, thienyl, furyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolyl, quinolyl, isoquinolyl, quinoxalinyl, bipyridyl, acridinyl, phenanthridinyl, phenanthrolinyl, quinazolinonyl, benzimidazolyl, benzofuranyl, benzothienyl, benzothiazolyl, benzoxazolyl, benzisoxazolyl, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, thiazinyl, or the following groups:

in some embodiments, R¹～R¹⁴At least one of (A) is NR¹⁷R¹⁸。

In some embodiments, R¹～R¹⁴In which 1 to 3 groups are NR¹⁷R¹⁸A group of (1).

In some embodiments, R²、R³、R⁶、R⁹、R¹²、R¹³At least one of (A) is NR¹⁷R¹⁸。

In some embodiments, R¹⁷And R¹⁸Independently is substituted or unsubstitutedSubstituted or unsubstituted aryl, substituted or unsubstituted heteroaryl;

in some embodiments, R¹～R¹⁴Wherein 1 to 10 groups other than hydrogen are present, preferably 2, 3, 4, 5 or 6, and the 1 to 10 groups other than hydrogen are each independently selected from fluorine, chlorine, bromine, iodine, cyano, or a substituted or unsubstituted group selected from the group consisting of: alkyl, alkoxy, aryl, aryloxy, trialkylsilyl or NR¹⁷R¹⁸。

In some embodiments, the R is¹～R¹⁸The 5-15 membered ring formed by any two adjacent groups or similar groups and the carbon atom in which the two adjacent groups or similar groups are located is 5-15 membered heteroaryl, 5-15 membered aryl, 5-15 membered heterocyclic group, 5-15 membered cycloalkyl or 5-15 membered unsaturated cycloalkyl; wherein, the hetero atom in the heteroaryl and heterocyclic radical is independently selected from nitrogen, sulfur or oxygen.

In some preferred embodiments, X²Is N, Y¹Is O, CR¹⁵R¹⁶Or S, in R¹～R¹⁶Wherein the definition of the R group at least satisfies one of the following: r⁶、R⁷At least one of (A) is halogen, C_1～4Alkyl radical, C_6～40Substituted or unsubstituted aryl, C_6～40A substituted or unsubstituted aryloxy group; r⁹Is hydrogen, deuterium, halogen, C_1～4Alkyl or C_6～40Substituted or unsubstituted aryl; r²、R³、R¹²、R¹³Independently hydrogen, deuterium, halogen, C_1～4Alkyl, NR¹⁷R¹⁸、C_6～40Substituted or unsubstituted aryl, C_6～40A substituted or unsubstituted aryloxy group; r¹⁵、R¹⁶Is a substituted or unsubstituted aryl group, and R¹⁵And R¹⁶Are directly connected or through a heteroatom O, S, NR¹⁹Wherein R is¹⁹Is substituted or unsubstituted alkyl, substituted or unsubstituted aryl.

In preferred further embodiments, X³Is N, Y¹Is O, CR¹⁵R¹⁶Or S, in R¹～R¹⁶Wherein the definition of the R group at least satisfies one of the following: r⁸、R⁹At least one of (A) is halogen, C_1～4Alkyl radical, C_6～40Substituted or unsubstituted aryl, C_6～40A substituted or unsubstituted aryloxy group; r¹⁵、R¹⁶Is a substituted or unsubstituted aryl group, and R¹⁵And R¹⁶Are directly connected or through a heteroatom O, S, NR¹⁹Wherein R is¹⁹Is substituted or unsubstituted alkyl, substituted or unsubstituted aryl.

In some embodiments, R is selected from the group consisting of¹～R¹⁴Or R¹～R¹⁶The total number of carbon atoms is 1 to 80, preferably 12 to 60, and more preferably 12 to 50.

In some embodiments, R¹⁷、R¹⁸Form a 5-7 membered heterocyclic ring or an aryl fused heterocyclic ring in a direct connection or in a connection through a bridge atom.

In other embodiments, NR¹⁷R¹⁸Is selected from Or a derivative group in which the hydrogen on these groups is substituted with one or more, the same or different substituents; wherein, Y²Is O, S, CR²⁰R²¹、SiR²²R²³、NR²⁴And R is²⁰～R²⁴Is hydrogen, deuterium, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl; wherein, the substituent in the derivative group is not particularly limited, and preferably, the derivative group is selected from: halogen, nitro, cyano trifluoromethyl, C_1～4Alkyl radical, C_1～4Alkoxy radical, C_1～4Alkylthio, 5-6 membered cycloalkyl, 5-6 membered heterocycloalkyl, aryl, aryloxy, heteroaryl, alkenyl, alkynyl, and wherein the substituents in the derivative group are independent of each other or one or more of any two of them are presentAnd 5-8 membered rings are formed by connecting adjacent groups.

In particular, NR¹⁷R¹⁸Some non-limiting examples of (a) are shown in the following structures:

in some embodiments, R¹～R¹⁶Any one of the groups containing carbon atoms, the number of carbon atoms being not more than 40.

In some embodiments, R¹～R¹⁶Any one of which does not contain an aryl group, and the number of carbon atoms of which is not more than 6.

In some embodiments, the tetradentate gold (III) complex is any one of the following compounds:

in some embodiments, the tetradentate gold (III) complex exhibits a photoluminescence quantum yield of 15% or greater in at least one medium, wherein the medium is a conventional organic solvent or transparent polymeric dispersion substrate in which the tetradentate gold (III) complex is soluble; conventional organic solvents are, for example: toluene, dichloromethane; examples of the transparent polymer-dispersed base material include: MCP films, PMMA films, and the like.

In some embodiments, the tetradentate metal (III) complex has an in-ligand charge transfer (ILCT) luminescence characteristic perturbed by a metal or has a TADF (thermally induced delayed fluorescence) luminescence characteristic.

In some embodiments, the tetradentate coordinated gold (III) complexes are used as light emitting materials or dopants in light emitting devices exhibiting a maximum external quantum efficiency EQE of 15% or more.

In some embodiments, tetradentate gold (III) complexes are provided that have low roll-off efficiency as light emitting materials or dopants for use in OLED light emitting devices.

In one embodiment, the emission luminance is up to 1000cd m^-2The tetradentate gold (III) complexes provided have roll-off efficiencies as low as 15%, and in one embodiment, emission luminances of up to 1000cd m^-2The tetradentate gold (III) complex provided, the efficiency is reduced to 11%, and in other embodiments, the emission luminance is up to 1000cd m^-2Meanwhile, the provided tetradentate coordination gold (III) complex is used as an OLED device prepared by a dopant, and the maximum external quantum efficiency of the OLED device is greater than or equal to 10%.

In other embodiments, the tetradentate gold (III) complex exhibits a photoluminescence quantum efficiency of greater than 40% in at least one of the media while having a wavelength of 5 × 10³s^-1The above radiation decay rate constants.

In other embodiments, the tetradentate gold (III) complex exhibits a photoluminescence quantum yield of 25% or greater and a photoluminescence quantum yield of 5X 10 in at least one of the organic solvents and at least one of the transparent polymeric dispersion substrate films, respectively and independently³s^-1The above radiation decay rate constants.

In other embodiments, the tetradentate gold (III) complex independently exhibits a photoluminescence quantum yield of greater than 25% in at least one organic solvent medium and at least one transparent polymeric dispersed substrate film, and simultaneously has a mass fraction of 5 × 10⁴s^-1The above radiation decay rate constants.

In other embodiments, the tetradentate coordinated gold (III) complexes are used as light emitting materials or dopants in light emitting devices exhibiting maximum external quantum efficiencies above 15%.

The invention also provides a preparation method of the tetradentate coordination gold (III) complex, which comprises the following steps:

mixing the tridentate coordination gold (III) complex with the structure of the formula (0-II) and a first solvent, and reacting under the microwave condition to obtain the structure of the formula (0-I);

or:

the following steps are executed in sequence:

a) reacting an organic compound with a structure shown in a formula (0-III) with a gold (III) reagent in a second solvent containing acid under the microwave condition to obtain an intermediate,

b) transferring the reaction product (namely the intermediate) in the step a) into a first solvent and reacting under the microwave condition to obtain the tetradentate coordination gold (III) complex with the structure of the formula (0-I).

Wherein the content of the first and second substances,

X¹、X²、X³independently selected from carbon or nitrogen, and X¹、X²、X³And only one of them is nitrogen;

X’¹、X’²、X’³independently selected from CH or nitrogen, and X'¹、X’²、X’³And only one of them is nitrogen;

Y¹is O, CR¹⁵R¹⁶Or S;

X_ais F, Cl, Br, I, OTf, OCOCOCF₃、OAc、OH、NTf₂；

R¹⁵、R¹⁶Independently selected from hydrogen, deuterium, halogen, nitro, cyano, isocyano, trifluoromethyl, or independently selected from substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, heteroaryloxy, NR¹⁷R¹⁸Acyl, acylamino, acyloxy, ester, amideA sulfonyl amino, sulfonyloxy, sulfonate, sulfonamide, or trialkylsilyl group; wherein R is¹⁷、R¹⁸Independently selected from the group consisting of substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, or heteroaryloxy;

or, R¹～R¹⁸Any two adjacent or similar groups and the carbon atom in which the two adjacent or similar groups are positioned form a 5-15-membered ring; wherein the 5-15 membered ring is 5-15 membered heteroaryl, 5-15 membered aryl, 5-15 membered heterocyclic group, 5-15 membered cycloalkyl or 5-15 membered unsaturated cycloalkyl; wherein the heteroatoms in the heteroaryl and heterocyclyl groups are independently selected from nitrogen, sulfur or oxygen.

A. B, C, D is independently substituted or unsubstituted aromatic ring, substituted or unsubstituted heteroaromatic ring, and when A, B, C, D contains a plurality of substituents on the ring, any two adjacent or close substituents can be connected to form a 5-8 membered ring; preferably, the A, B, C, D is independently substituted or unsubstituted C_6～40Aromatic ring of (2), substituted or unsubstituted C_5～40The heteroaromatic ring of (a).

In some embodiments, when ring A, B, C, D contains substituents, these substituents are selected from the group consisting of: deuterium, halogen, nitro, nitroso, cyano, isocyano, trifluoromethyl, or a substituted or unsubstituted group selected from: alkyl, heteroalkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocyclyl, alkanoyl, aroyl, alkoxy, aryloxy, NR¹⁷R¹⁸An ester group, an amide group, a sulfonamide group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group; alkylsilyl, arylsilyl, haloalkyl, arylalkyl.

In some embodiments, the method of making specifically comprises: under the promotion of microwaves, enabling the tridentate coordination base gold (III) complex with the structure of the formula (0-II) to perform intramolecular Au-C (gold-carbon bond) coupling reaction based on C-H (carbon-hydrogen bond) activation in a first solvent to obtain the structure of the formula (0-I), wherein the intramolecular Au-C coupling reaction based on C-H activation refers to activation and breakage of C-H before or during the intramolecular Au-C coupling reaction.

In some embodiments, the structure of formula (II) is prepared according to the following literature:

reacting an organic compound with a structure shown in a formula (0-III) with Hg (II) reagent and gold (III) reagent in sequence to obtain a tridentate coordination gold (III) complex with the structure shown in the formula (0-II); the reaction does not require microwaves.

In other embodiments, the method of preparation specifically comprises: a) under the promotion of microwaves, enabling an organic compound with a structure shown in a formula (0-III) and a gold (III) reagent to perform intermolecular coordination coupling reaction based on C-H activation in a second solvent containing acid to obtain an intermolecular coordination coupling reaction product; b) subjecting the intermolecular coordination coupling reaction product of step a to intramolecular Au-C coupling reaction based on C-H activation in a first solvent under the promotion of microwaves to obtain the complex with the structure of formula (0-I), wherein the intermolecular coordination coupling reaction based on C-H activation comprises: intermolecular Au-N coordination reactions and intermolecular Au-C coupling reactions involving activation and cleavage of C-H.

The invention also provides a preparation method of the gold (III) complex, which comprises the following steps:

reacting a mixture of a tridentate coordination gold (III) complex with a structure shown in a formula (II) and a first solvent under the microwave condition to obtain a structure shown in a formula (I);

or, the following steps are executed in sequence:

a) reacting an organic compound with a structure shown in a formula (III) with a gold (III) reagent in a second solvent containing acid under the microwave condition to obtain an intermediate,

b) transferring the intermediate obtained in the step a) into a first solvent and reacting under the microwave condition to obtain a tetradentate coordination gold (III) complex with a structure shown in a formula (I);

the utility model is provided with a first cover,

X¹、X²、X³independently selected from carbon or nitrogen, and X¹、X²、X³And only one of them is nitrogen;

X’¹、X’²、X’³independently selected from CH or nitrogen, and X'¹、X’²、X’³And only one of them is nitrogen;

Y¹is O, CR¹⁵R¹⁶Or S;

X_ais F, Cl, Br, I, OTf, OCOCOCF₃OAc, OH or NTf₂；

R¹～R¹⁶Independently selected from hydrogen, deuterium, halogen, nitro, cyano, isocyano, trifluoromethyl, or independently selected from substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, heteroaryloxy, NR¹⁷R¹⁸An acyl group, an acylamino group, an acyloxy group, an ester group, an acylamino group, a sulfonamido group, a sulfonyloxy group, a sulfonate ester, a sulfonamide or a trialkylsilyl group; wherein R is¹⁷、R¹⁸Independently selected from the group consisting of substituted or unsubstituted: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, aralkyl, heteroalkyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroaralkyl, alkoxy, aryloxy, or heteroaryloxy;

or, R¹～R¹⁸Any two adjacent or similar groups and the carbon atom in which the two adjacent or similar groups are located form a 5-15-membered ring.

The present invention provides the above-mentioned preparation process wherein each substituent is selected in the same range as that of the substituents in the definition of the aforementioned ligand, and in some embodiments, X_aIs Br, Cl, OH, OCOCF₃Or an OAc.

In some embodiments, the first solvent is water or a mixed solvent of water and one or more organic solvents selected from the group consisting of ACN, DMF, DMA, THF, and 1, 4-dioxane in any ratio, preferably a mixed solvent of water and ACN, wherein water and ACThe volume ratio of N is 3: 1-1: 3, and H is more preferable₂The volume ratio of O to ACN is 1.5: 1-1: 1.5.

In some embodiments, the reaction carried out in the first solvent (referred to herein as an intramolecular Au-C coupling reaction) has a reaction temperature of 100 to 170 ℃.

In some embodiments, the reaction time of the intramolecular Au-C coupling reaction is 10 to 100 min.

In some embodiments, the reaction temperature of the intramolecular Au-C coupling reaction using the structure of formula II as the starting material is 110-130 ℃, and the reaction time is 10-40 min, preferably 20-30 min.

In some embodiments, the reaction temperature of the intramolecular Au-C coupling reaction (i.e., the reaction of step b) using the reaction product (i.e., the intermediate) of step a as the starting material is 120 to 170 ℃, preferably 130 to 150 ℃, and the reaction time is 50 to 100min, preferably 70 to 90 min.

In some embodiments, the molar ratio of the tridentate gold (III) complex (structure of formula II) or intermediate to the first solvent is between 10% and 0.1%, preferably between 2% and 0.5%.

In some embodiments, the reaction further comprises a post-treatment purification step after the reaction; further, the step of post-treatment purification comprises the steps of organic phase/aqueous phase extraction and column purification.

In some embodiments, the gold (III) reagent is selected from Au (OAc)₃、AuCl₃、Au(OTf)₃、HAuCl₄、KAuCl₄、NaAuCl₄、KAuBr₄、NaAuBr₄Preferably Au (OAc)₃。

In some embodiments, the acid in the acid-containing second solvent is AcOH, TFA, TfOH, TsOH, HF, HCl, HBr.

In some embodiments, the second solvent is a solvent obtained by mixing one or more of water, conventional alcohol solvents including, but not limited to, methanol, ethanol, isopropanol, acetonitrile, DMF, DMSO, DMA, THF, and 1, 4-dioxane in any ratio.

In some preferred embodiments, the second solvent is a mixed solvent of TFA/water, TFA/ethanol, TFA/methanol, AcOH/water, HCl/water, TFA/ethanol/water, TFA/methanol/water, TFA/ACN/water.

In some preferred embodiments, the volume ratio of the acid in the second solvent to the remaining solvent is from 10: 1 to 1: 10; preferably 2: 1 to 1: 2.

In some embodiments, the reaction temperature in step a is 110-170 ℃, preferably 120-140 ℃.

In some embodiments, the reaction time of step a is 20 to 50 min.

In some embodiments, after the reaction of step a is finished, extracting with an organic solvent and concentrating to obtain an intermediate; can be used directly in the preparation reaction of step b without further purification.

In some embodiments, the reaction of step a further comprises adding an alkali metal trifluoroacetate, such as CF, to the reaction system₃COONa、CF₃COOK, preferably, the addition amount of the trifluoroacetic acid alkali metal salt is 3-5 times of that of the gold (III) reagent in the same system by mol; preferably, when the alkali metal trifluoroacetate is added, the preferable reaction system adopts AcOH/H with the volume ratio of 2: 1-1: 2₂O as a second solvent.

In some embodiments, when R¹～R¹⁴When at least one of them is halogen, the process for preparing the tetradentate gold (III) complex further comprises a step of converting the R group, which is halogen, to a non-halogen group, which may be NR, for example¹⁷R¹⁸。

The tridentate gold (III) complexes of the structure of formula (II) of the present invention may be obtained from organic compounds of the structure of formula (III) by conventional or literature-documented multi-step reactions, which, for example, in one embodiment, comprise, in sequence: in the presence of Hg (II) reagent, organic compound with the structure of formula (III) undergoes C-H activation reaction to obtain ligand-Hg (II) compound, and then Au (III) and Hg (II) undergo metal displacement reaction in the presence of gold (III) reagent to obtain tridentate gold (III) complex, wherein the Hg (II) reagent includes but is not limited to HgCl₂、Hg(OAc)₂Gold (III) reagents include, but are not limited to, KAuCl₄、NaAuCl₄、HAuCl₄、Au(OAc)₃、AuCl₃、KAuBr₄、NaAuBr₄、Au(OTf)₃. In one embodiment, the multi-step reaction further comprises: after the metal displacement reaction has taken place, HX^aOr a salt of an acid ion thereof (e.g., a silver salt CF of an acid ion thereof)₃COOAg) form of X_aThe metathesis reaction of (1).

In order to achieve the object of the present invention, the present invention also provides a tridentate gold (III) complex of the formula (II) which can be used for preparing a structure of the formula (I),

wherein, X_aIs F, Cl, Br, I, OTf, OCOCOCF₃、OAc、OH、NTf₂；

X¹～X³、Y¹、R¹～R¹⁴As defined above.

In order to achieve the aim of the invention, the invention also provides an organic compound shown in a formula (III) which can be used for preparing the structure shown in the formula (I),

wherein, X'¹～X’³Optionally (c): one X 'is a N atom and two X' are CH; y is¹、R¹～R¹⁴As defined above.

In order to achieve the object of the present invention, the present invention also provides an application of the gold (III) complex of the present invention in the preparation of a light emitting device.

In order to achieve the object of the present invention, the present invention also provides a light emitting device comprising a light emitting layer, the light emitting layer being the gold (III) complex according to the present invention.

To achieve the object of the present invention, the present invention proposes a light-emitting device comprising a tetradentate gold (III) complex having a structure represented by formula I as defined above.

In some embodiments, the light emitting device comprises: the organic electroluminescent device comprises a substrate, an anode Layer, a Hole injection Layer, a Hole Transport Layer (HTL), an Emitting Layer (EML), an Electron Transport Layer (ETL), an Electron injection Layer and a cathode Layer, wherein the tetradentate coordination gold (III) complex is positioned in the Emitting Layer EML; specifically, the structure of the light emitting device is shown in fig. 1, and fig. 1 shows a structural diagram of the light emitting device according to an embodiment of the present invention.

In some embodiments, the light emitting device exhibits a maximum external quantum efficiency of 13 to 25%; preferably, in some embodiments, the light emitting device exhibits a maximum external quantum efficiency of 20 to 25%; preferably, in some embodiments, the light emitting device exhibits an external quantum efficiency of greater than 20%, including but not limited to greater than 21%, 22%, 23%, 24%, 25%.

In some embodiments, the light emitting device OLED has a low roll-off efficiency; in one embodiment, the emission luminance is up to 1000cd m^-2When the light emission luminance reaches 1000cd m, the roll-off of the efficiency is less than 12%, and in another embodiment^-2Efficiency roll-off is less than 11%, and in other embodiments, the emission luminance is up to 1000cd m^-2When the tetradentate coordination gold (III) complex is used as a dopant, the prepared OLED device can keep the external quantum efficiency of more than 10%.

In some embodiments, a hole-blocking layer is further included between the light-emitting layer and the electron-transporting layer;

in some embodiments, the light-emitting layer comprises one or more layers, and the tetradentate gold (III) complex provided herein is located in at least one of the light-emitting layers.

Specifically, the light-emitting layer may be prepared by vacuum evaporation, a solution method, or an inkjet printing method to form a film containing the tetradentate-coordinated gold (III) complex.

The technical scheme provided by the invention at least meets at least one of the following conditions:

the tetradentate ligand provided by the invention is coordinated with gold (III) to form a tetradentate coordination gold (III) complex, and the tetradentate coordination gold (III) complex is used as a luminescent material or a luminescent device of an OLED (organic light emitting diode) made of a dopant, shows high luminescent brightness, electroluminescent efficiency and external quantum efficiency, and has the maximum current efficiency up to 78cd A measured^-1The maximum external quantum efficiency EQE is basically more than 15 percent and can reach 25 percent at most, the EQE is basically kept more than 11 percent and can reach 22 percent at 1000 brightness value, the efficiency is reduced to 11 percent, and the organic light-emitting material is a novel organic light-emitting material potentially applied to OLEDs.

In addition, the complexes with the same parent nucleus structure have better universality on the luminescence property, and the luminescence color of the complexes can be adjusted by adjusting the types and the positions of substituents on the parent nucleus and combining with the use of dispersion media with different polarities.

The invention provides a novel preparation method of a tetradentate gold (III) complex, which utilizes microwave-promoted C-H activation and intramolecular Au-C coupling reaction and combines microwave-promoted intermolecular coordination coupling reaction as necessary to obtain a target product with a 5-5-6 rigid ring structure with moderate to excellent yield.

In other embodiments, the tetradentate gold (III) complex exhibits a photoluminescence quantum efficiency of greater than 40% in at least one of the media while having a wavelength of 5 × 10³s^-1The above radiation decay rate constants.

In other embodiments, the tetradentate gold (III) complex is present in at least one of the organic solvents and at least one of the transparent polymeric dispersion substrate films independentlyShows a photoluminescence quantum yield of 25% or more and 5X 10³s^-1The above radiation decay rate constants.

In other embodiments, the tetradentate gold (III) complex independently exhibits a photoluminescence quantum yield of greater than 25% in at least one organic solvent medium and at least one transparent polymeric dispersed substrate film, and simultaneously has a mass fraction of 5 × 10⁴s^-1The above radiation decay rate constants.

In other embodiments, the tetradentate coordinated gold (III) complexes are used as light emitting materials or dopants in light emitting devices exhibiting maximum external quantum efficiencies above 15%.

Definition of

To facilitate an understanding of the invention, some terms, abbreviations or other abbreviations used herein are defined as follows, unless otherwise indicated.

"alkyl", alone or in combination with other groups, represents a saturated straight or branched chain group containing 1 to 12 carbon atoms, such as: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, and n-decyl, and the like.

"alkenyl", alone or in combination with other groups, represents a straight or branched chain group containing 2 to 12 carbon atoms and containing unsaturated double bonds, including straight or branched chain dienes such as: vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, 1, 3-butadiene, 1, 3-pentadiene, 2-methyl-1, 3-butadiene and the like.

"alkynyl", alone or in combination with other groups, represents ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, straight or branched diyne or triyne, e.g. 1, 3-diacetylene, which may be further substituted by aryl.

"cycloalkyl", alone or in combination with other groups, represents a 3-to 7-membered carbocyclic group such as: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

"cycloalkenyl", alone or in combination with other groups, represents a 3-7 membered cyclic group containing more than one unsaturated double bond, such as: a cycloalkenylpropyl group, a 1-cyclobutenyl group, a 2-cyclobutenyl group, a 1-cyclopentenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group, a 1, 3-cyclopentadienyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, a 3-cyclohexenyl group, a 1, 3-cyclohexadienyl group, a cycloheptenyl group, a cycloheptadienyl group, a cycloheptatrienyl group and the like.

"aryl" or' "aromatic", alone or in combination with other groups, refers to an optionally substituted aromatic carbocyclic group containing 1, 2 or 3 rings linked by bonds or by fusion between said rings, for example: phenyl, biphenyl, naphthyl, tetralin, indane, which may be further substituted with other aryl or aryl-containing substituents.

"Heterocyclyl" or "heterocycle", alone or in combination with other groups, represents an optionally substituted 3-to 7-membered cyclic group containing one or more heteroatoms selected from N, S and O, including saturated, partially saturated, and aromatic unsaturated heterocyclic groups. Saturated heterocyclic groups, which are herein referred to by the term "heterocycloalkyl", alone or in combination with other groups, include, for example: aziridinyl, azetidinyl, tetrahydrofuryl, tetrahydrothienyl, oxazolidinyl, thiazolidinyl, benzothiazolyl, pyrrolidinyl, imidazolidinyl, piperidinyl, piperazinyl, thiazinyl, 2-oxopiperidinyl, 4-oxopiperidinyl, 2-oxopiperazinyl, 3-oxopiperazinyl, morpholinyl, thiomorpholinyl, 2-oxomorpholinyl, azaRadical diazaOxygen radical and oxygen radicalBasic, sulfur heteroAnd 1 to 3 oxacyclohexane groups. The partially saturated heterocyclic group, which is referred to herein as the term "heterocycloalkenyl", alone or in combination with other groups, includes, for example, dihydrothiophene, dihydropyran, dihydrofuran, dihydrothiazole, and the like. Aromatic unsaturated heterocyclic groups, which correspond to the terms "heteroaryl" or "heteroaromatic" in this context, alone or in combination with other groups, may be monocyclic or may be linked or fused polycyclic, examples of which include: thiazolyl, oxazolyl, imidazolyl, isoxazolyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, thienyl, furyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolyl, quinolyl, isoquinolyl, quinoxalinyl, bipyridyl, acridinyl, phenanthridinyl, phenanthrolinyl, quinazolinonyl, benzimidazolyl, benzofuranyl, benzothienyl, benzothiazolyl, benzoxazolyl, benzisoxazolyl, bipyridyl, biphenylpyridyl.

"heteroalkyl," alone or in combination with other groups, represents a straight or branched chain alkyl group containing more than one heteroatom selected from N, S and O, examples of which include: methoxymethyl, methoxyethyl, 2-methoxypropyl, dimethylaminoethyl, 2-methylthiobutyl and the like.

Herein, unless otherwise specified, the "heteroalkyl group" or "heterocyclic group" contains one or more, preferably 1 to 6, more preferably 1, 2 or 3 heteroatoms, and when there are a plurality of the heteroatoms, the plurality of the heteroatoms may be the same or different.

"halogen", alone or in combination with other groups, such as "haloalkyl", "perhaloalkyl", and the like, refers to fluoro, chloro, bromo, or iodo. The term "haloalkyl" represents an alkyl group as defined above substituted with one or more halogens, including perhaloalkyl groups, for example: fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, trifluoroethyl and the like. The term "haloalkoxy" represents a haloalkyl group as defined above directly attached to an oxygen atom, for example fluoromethoxy, chloromethoxy, fluoroethoxy, chloroethoxy and the like.

"acyl", alone or in combination with other groups, includes some of the following forms: -C (═ O) H, -C (═ O) -alkyl, -C (═ O) -aryl, -C (═ O) -aralkyl, and-C (═ O) -heteroaryl, such as formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, benzoyl, and the like, the non-C (═ O) -moiety on the acyl group may be substituted with an optional substituent, including but not limited to, halogen, lower alkyl (C1 to C4 alkyl), aryl, or aryl-containing substituents.

"esters" are a class of carboxylic acid derivatives, which, alone or in combination with other groups, represent the group-COO-, and include: alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl and the like; aryloxycarbonyl groups such as phenoxycarbonyl, naphthyloxycarbonyl, and the like; aralkoxycarbonyl such as benzyloxycarbonyl, phenethyloxycarbonyl, naphthylmethoxycarbonyl; heterocyclyloxycarbonyl, wherein heterocyclyl is as defined above; the non-COO-moiety on the ester group may be further substituted with an optional substituent.

"acyloxy", alone or in combination with other groups, means an acyl group as defined above attached directly to an oxygen atom, for example: -O-C (═ O) -alkyl, -O-C (═ O) -aryl, -O-C (═ O) -aralkyl, specifically, for example, acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, benzoyloxy and the like.

"monosubstituted amino", alone or in combination with other groups, means an amino group substituted with a group selected from substituted or unsubstituted C1-C6 alkyl, aryl or aralkyl, for example, methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, aniline, and the like, and may be further substituted.

"disubstituted amino", alone or in combination with other groups, represents an amino group substituted by two groups which may be the same or different, said substituents being selected from the group consisting of substituted or unsubstituted: (C1-C6) alkyl, aryl or arylalkyl groups, such as dimethylamino, methylethylamino, diethylamino, phenylmethylamino, diphenylamino, and the like, which may be further substituted.

"amides", alone or in combination with other groups, represent aminocarbonyl groups of the general formula-C (═ O) -N (group) 2, mono-or disubstituted aminoacyl groups as defined above, for example: n-methylamides, N-dimethylamides, N-ethylamides, N-ethyl-N-phenylamides, N-diphenylamides.

"acylamino", alone or in combination with other groups, represents an acyl group as defined above linked to an amino group, which may be, for example, CH₃CONH-、C₂H₅CONH-、C₃H₇CONH-、C₄H₉CONH-、C₆H₅CONH-, etc., which may be substituted.

"MW", "Microwave" refer to the Microwave technology used in the experiment, the type of Microwave reactor used in the experiment being "CEM Discover SP".

As used herein to describe a compound or chemical moiety as being "substituted" means that at least one hydrogen atom of the compound or chemical moiety is replaced with a second chemical moiety. Non-limiting examples of substituents are those present in the exemplary compounds and embodiments disclosed herein, as well as tritium, fluorine, chlorine, bromine, iodine; hydroxy, oxo; amino (primary, secondary, tertiary), imino, nitro, nitroso; cyano, isocyano, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkenyl, cycloalkenyl, alkynyl; lower alkoxy, aryloxy; mercapto, thioether; a phosphine; carboxyl, sulfonic acid group, phosphonic acid group; acyl, thiocarbonyl, sulfonyl; amides, sulfonamides; a ketone; an aldehyde; esters, sulfonates; haloalkyl (e.g., difluoromethyl, trifluoromethyl); a carbocyclic alkyl group which may be monocyclic or fused or non-fused polycyclic (e.g., cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl); or a heterocycloalkyl group which may be a single ring or fused or non-fused polycyclic (e.g., pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, or thiazinyl); or a carbocyclic or heterocyclic aryl group which may be monocyclic or fused or non-fused polycyclic (e.g. phenyl, naphthyl, thiazoleA group selected from the group consisting of an oxazolyl group, an imidazolyl group, an isoxazolyl group, a pyrrolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a thienyl group, a furyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, an indolyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a bipyridyl group, an acridinyl group, a phenanthridinyl group, a phenanthrolinyl group, a quinazolinonyl group, a benzimidazolyl group, a benzofuranyl group, a benzothienyl group, a benzothiazolyl group, a benzoxazolyl group, a benzisoxaz; or can also be: aryl-lower alkyl; -CHO; -CO (alkyl); -CO (aryl); -CO₂(alkyl); -CO₂(aryl); -CONH₂；-SO₂NH₂；-OCH₂CONH₂；-OCHF₂；-OCF₃；-CF₃；-NH₂(ii) a -NH (alkyl); -N (alkyl)₂(ii) a -NH (aryl); -N (alkyl) (aryl); -N (aryl)₂(ii) a Further, when the substituent is oxygen, it means that two hydrogen atoms on the same or different carbons are substituted with the same oxygen atom to form a carbonyl group or a cyclic ether, such as a ketocarbonyl group, an aldehyde carbonyl group, an ester carbonyl group, an amide carbonyl group, ethylene oxide, etc.; in addition, these moieties may also be optionally substituted with fused ring structures or bridges (e.g., -OCH 2O-). In the present invention, it is preferred that one, two, three, four, five or six substituents independently selected from halogen, alkyl, alkoxy, aryl, aryloxy, -N (aryl) 2, such as trifluoromethyl, perfluorophenyl, are substituted or perhalosubstituted, and, when the substituents contain hydrogen, these substituents may be optionally further substituted by a substituent selected from such groups.

As used herein, describing a compound or chemical moiety as being "independently" should be understood as meaning that the plurality of compounds or chemical moieties defined before the term should each enjoy the selection ranges provided thereafter equally, without interfering with each other, and should not be understood as defining any spatial connection relationship between the various groups; spatially connected relationships are referred to herein by the terms "independently of one another," "connected," and the like; should be distinguished; in the present invention, "independently" and "independently each other" and "independently selected from" have substantially the same meaning.

As used herein, the description of two "adjacent" chemical moieties being linked to form a cyclic structure should be understood to include both the situation where two chemical moieties are positionally adjacent, illustratively including the situation where two groups on the same aromatic ring are in the ortho position, and the situation where two groups are sterically adjacent, illustratively including the situation where two groups are on different linked or fused aromatic rings, but can be in close spatial proximity to each other.

In the present application, "singlet" is sometimes referred to as "singlet", and correspondingly, "triplet" is sometimes referred to as "triplet".

For ease of understanding and to avoid confusion, in the present application, the "structure of formula (III)" represents the structural formula numbered III, and "gold (III)" or "au (III)" each represents metallic gold having a valence state of + 3.

Unless otherwise specified, "OLED" as used herein refers to an organic light emitting diode, and thus, in the present application, "OLED" is sometimes also referred to as "OLED device" or "OLED light emitting device" or "OLED apparatus" or "OLED light emitting apparatus".

Furthermore, for the purposes of clarity and ease of understanding of the present invention, the present disclosure or embodiments are provided in relation to chinese references to chemical abbreviations, as follows:

ACN represents acetonitrile; DMF means N, N-dimethylformamide; DMA represents N, N-dimethylacetamide; THF represents tetrahydrofuran; DMSO, DMSO: represents N, N-dimethyl sulfoxide; TFA represents trifluoroacetic acid; TfOH for trifluoromethanesulfonic acid; TsOH represents p-toluenesulfonic acid; AcOH represents acetic acid, also called acetic acid; pd (dba)₂Represents bis-dibenzylideneacetone palladium; KOAc represents potassium acetate; pd (dppf) Cl₂Represents [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride; pd (PPh)₃)₄Represents tetrakis (triphenylphosphine) palladium; binap represents (±) -2, 2 '-bis- (diphenylphosphino) -1, 1' -binaphthyl; KO (Ko)^tBu represents potassium tert-butoxide; TCTA denotes 4, 4', 4 ″ -tris (carbazol-9-yl) triphenylamine; TAPC represents 4, 4' -cyclohexylbis (N, N-bis (4-methylphenyl) aniline); TPBi represents 1, 3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene; TmPyPb represents 3, 3 '- [ 5' - [3- (3-pyridyl) phenyl][1, 1 ': 3 ', 1 ' -triadBenzene and its derivatives]-3, 3 "-diyl]Bipyridine; HAT-CN represents 2, 3, 6, 7, 10, 11-hexacyano-1, 4, 5, 8, 9, 12-hexaazatriphenylene; T2T: represents 2, 4, 6-tris (1, 1' -biphenyl) -1, 3, 5-triazine; ITO represents indium tin oxide

In order to further illustrate the present invention, the following examples are given to illustrate the complexes provided by the present invention in detail, but they should not be construed as limiting the scope of the present invention. Unless otherwise specified, all percentages referred to in the examples are by weight and all solvent mixture proportions are by volume.

Preparation of ligand Compounds and precursors thereof

Example 1 preparation of L1

To a reaction flask was added precursor 111(2.65g, 9.00mmol), precursor 112(5.04g, 9.90mmol), excess ammonium acetate NH₄The mixture was refluxed for 12 hours with AcOH acetate, cooled to room temperature, extracted with water/dichloromethane, the organic phase was washed with water several times to remove the acid, dried over anhydrous magnesium sulfate, and then the solvent was removed using a rotary evaporator to give a crude product, which was purified by silica gel column chromatography (dichloromethane/hexane ═ 1: 6) to give substantially pure l 12.86g, yield 55%.

¹H NMR(500MHz，CD₂Cl₂)：δ8.06(d，J＝8.5Hz，2H)，7.89(d，J＝1.5Hz，1H)，7.78(d，J＝1.5Hz，1H)，7.71(d，J＝8.5Hz，2H)，7.65(d，J＝2.5Hz，2H)，7.52(d，J＝8.5Hz，2H)，7.37(t，J＝8.0Hz，4H)，7.14(t，J＝7.5Hz，2H)，7.10(d，J＝8.0Hz，4H)，7.05(d，J＝9.0Hz，2H)，6.72(t，J＝2.5Hz，1H)，3.87(s，3H)，1.37(s，9H).¹³C NMR(100MHz，CD₂Cl₂)：δ161.05，159.17，157.60，157.37，156.15，152.80，150.06，143.23，131.25，130.27，128.69，127.05，126.03，123.97，119.31，117.08，116.67，114.87，112.92，110.26，55.77，35.00，31.45.EI-MS：m/z 577.2584[M]⁺.

Among them, the precursor 111 and the precursor 112 can be prepared according to the following reaction formulae and existing conventional reaction conditions.

Example 2 preparation of L2

In a similar manner as described for preparation L1, precursor 211(5.31g, 10.51mmol), precursor 212(4.68g, 11.57mmol), excess ammonium acetate NH were added to the reaction flask₄The mixture was refluxed for 12 hours with AcOH acetate, cooled to room temperature, extracted with water/dichloromethane, the organic phase was washed with water several times to remove the acid, dried over anhydrous magnesium sulfate, and then the solvent was removed using a rotary evaporator to give a crude product, which was purified by silica gel column chromatography (dichloromethane/n-hexane ═ 1: 6) to give substantially pure l 23.23g in 45% yield.¹H NMR(500MHz，CD₂Cl₂)：δ8.15(d，J＝8.5Hz，2H)，8.01(s，1H)，7.94(s，1H)，7.76(d，J＝2.0Hz，2H)，7.71-7.68(m，3H)，7.66(d，J＝1.5Hz，2H)，7.45(t，J＝8.0Hz，4H)，7.24-7.21(m，6H)，6.81(t，J＝2.0Hz，1H)，1.52(s，18H).¹³C NMR(125MHz，CD₂Cl₂)：δ159.57，157.24，156.42，156.36，152.36，142.85，138.73，138.70，132.26，130.37，129.12，124.26，123.98，123.89，122.06，119.98，119.73，118.36，118.07，112.52，110.09，35.48，31.82.EI-MS：m/z 681.2187[M]⁺.

Among them, the precursor 211 and the precursor 212 can be prepared according to the following reaction formulae and existing conventional reaction conditions.

Under the protection of nitrogen, the reaction flask is filled with the mixtureTo the mixture were added acetophenone (1.23g, 10.25mmol) and KO^tBu (2.30g, 20.50mmol) and anhydrous tetrahydrofuran were stirred at room temperature for about 2 hours, then a solution of the precursor 311(2.89g, 10.25mmol) in anhydrous tetrahydrofuran was added to the reaction system, and stirred at room temperature for about 12 hours, and then excess ammonium acetate NH was added₄OAc and AcOH acetate, heated to reflux for 12 hours, cooled to room temperature, subjected to water/dichloromethane extraction, the organic phase washed with water several times to remove the acid, the organic phase dried over anhydrous magnesium sulfate, and then the solvent removed using a rotary evaporator to give a crude product, which was purified by silica gel column chromatography (dichloromethane/hexane ═ 1: 6) to give substantially pure l 32.04g in 59% yield.

¹H NMR(500MHz，CD₂Cl₂)：δ8.09-8.07(m，2H)，7.83(t，J＝7.5Hz，1H)，7.74(dd，J＝8.0，0.5Hz，1H)，7.50-7.46(m，2H)，7.44-7.41(m，1H)，7.37-7.32(m，3H)，7.30(d，J＝8.5Hz，1H)，7.18(d，J＝2.5Hz，1H)，7.08(tt，J＝7.0，1.5Hz，1H)，7.07-7.04(m，2H)，6.99(dd，J＝8.5，2.5Hz，1H)，2.44(s，3H).¹³C NMR(125MHz，CD₂Cl₂)：δ159.45，158.08，156.72，155.45，142.36，139.76，137.55，132.51，131.67，130.13，129.37，129.08，127.27，123.42，122.76，120.71，119.25，118.90，118.72，20.09.EI-MS：m/z 337.1446[M]⁺.

Among them, the precursor 311 can be prepared according to the following reaction formula and conventional reaction conditions.

In a similar manner as described for preparation L3, acetophenone (1.54g, 12.79mmol), KO and nitrogen were added to a reaction flask^tBu (2.87g, 25.60mmol) and anhydrous tetrahydrofuran were stirred at room temperature for about 2 hours, then a solution of the precursor 411(3.43g, 12.79mmol) in anhydrous tetrahydrofuran was added to the reaction system, and stirred at room temperature for about 12 hours, and then excess ammonium acetate NH was added₄OAc and AcOH acetic acid, heated to reflux for 12 hoursAfter cooling to room temperature, water/dichloromethane extraction was performed, the organic phase was washed with water several times to remove the acid, and the organic phase was dried over anhydrous magnesium sulfate, and then the solvent was removed using a rotary evaporator to obtain a crude product, which was subjected to silica gel column chromatography (dichloromethane/n-hexane ═ 1: 6) to obtain substantially pure l4212.57g with a yield of 62%.¹H NMR(500MHz，CD₂Cl₂)：δ8.11(d，J＝7.5Hz，2H)，7.85(d，J＝8.0Hz，1H)，7.74(t，J＝8.0，1H)，7.67(d，J＝2.5Hz，1H)，7.55-7.44(m，4H)，7.36(d，J＝7.5Hz，1H)，7.23(d，J＝8.0Hz，1H)，2.42(s，3H).¹³C NMR(125MHz，CD₂Cl₂)：δ158.55，157.02，142.95，139.86，139.63，137.97，137.60，135.71，132.75，131.38，129.44，129.09，127.28，122.75，118.96，20.33.EI-MS：m/z 323.0275[M]+。

Among them, the precursor 411 can be prepared according to the following reaction formula and existing conventional reaction conditions.

Precursor 421(2.57g, 7.93mmol), KOAc (2.33g, 23.79mmol), Pd (dppf) Cl were added to the reaction flask under nitrogen protection₂(0.58g, 0.79mmol), bis (pinacolato) borate (4.03g, 15.86mmol) and anhydrous 1, 4-dioxane, the mixture was heated under reflux for 24 hours, the solvent was removed using a rotary evaporator, water/dichloromethane extraction was performed, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator and the crude product was obtained, and 4311.62g of a substantially pure precursor was obtained by silica gel column chromatography (dichloromethane/n-hexane ═ 1: 6) with a yield of 55%.¹H NMR(500MHz，CD₂Cl2)：68.14(d，J＝7.5Hz，2H)，7.95(s，1H)，7.83(q，J＝7.5，2H)，7.74(d，J＝8.0Hz，1H)，7.52(t，J＝7.5Hz，2H)，7.46(d，J＝7.5Hz，1H)，7.41(t，J＝7.0Hz，2H)，2.54(s，3H).¹³C NMR(125MHz，CD₂Cl₂)：δ160.25，156.67，140.66，140.05，139.94，137.47，136.50，134.97，130.77，129.33，129.09，127.33，122.90，118.51，84.16，83.64，25.20，21.13.EI-MS：m/z 371.2031[M]⁺。

The precursor 431 obtained above was dissolved in tetrahydrofuran, the mixture was placed in an ice bath, hydrogen peroxide in an amount of 30% by mass was added to the mixture and stirred at room temperature, the progress of the reaction was checked by TLC, after the reaction was completed, the solvent was removed using a rotary evaporator, water/dichloromethane extraction was performed, the organic phase was washed several times to remove excess hydrogen peroxide and dried over anhydrous magnesium sulfate, and then the solvent was removed using a rotary evaporator to obtain 4411.00 g of the precursor, with a yield of 88%.¹H NMR(500MHz，CD₂Cl2)：δ8.07(d，J＝7.5Hz，2H)，7.83(t，J＝8.0Hz，1H)，7.72(dd，J＝8.0，0.5，1H)，7.51-7.43(m，3H)，7.32(d，J＝7.5Hz，1H)，7.11(d，J＝8.0Hz，1H)，6.89(d，J＝3.0Hz，1H)，6.71(dd，J＝8.5，3.0Hz，1H)，3.81(s，1H)，2.34(s，3H).¹³C NMR(125MHz，CD₂Cl₂)：δ160.05，157.04，154.60，141.40，139.73，137.65，132.04，129.37，129.06，127.71，127.50，122.98，119.14，117.24，116.00，19.69.EI-MS：m/z 261.1130[M]⁺。

Example 6 preparation of L4

A reaction flask was charged with precursor 441(1.00g, 3.83mmol), CuI (0.07g, 0.38mmol), Cs under nitrogen blanket₂CO₃(3.74g, 11.49mmol), N-dimethylglycine (0.08g, 0.76mmol) and anhydrous 1, 4-dioxane, the mixture was heated under reflux for 24 hours, the solvent was removed using a rotary evaporator, water/dichloromethane extraction was performed, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator to give a crude product, and substantially pure l 40.99g was obtained by silica gel column chromatography (dichloromethane/N-hexane ═ 1: 5) with a yield of 62%.¹H NMR(300MHz，CD₂Cl₂)：δ8.18-8.14(m，2H)，7.83(t，J＝7.5Hz，1H)，7.77(dd，J＝7.8，0.9Hz，1H)，7.57-7.44(m，3H)，7.41-7.36(m，2H)，7.32-7.20(m，4H)，7.09-7.03(m，2H)，2.53(s，3H).¹³C NMR(100MHz，CD₂Cl₂)：δ159.20，159.12，156.69，154.49，142.52，139.63，137.54，132.76，132.49，131.31，129.41，129.09，127.26，126.23，123.18，122.72，121.61，121.26，119.73，118.73，117.28，20.28.EI-MS：m/z 415.0537[M]⁺.

Example 7 preparation of precursor 511

2-bromo-4, 4' -di-tert-butylbiphenyl (3.47g, 10.05mmol) and anhydrous tetrahydrofuran were charged into a reaction flask under nitrogen protection, the mixture was cooled to-78 ℃ and kept at this temperature for stirring for 5 minutes, a 2.4M solution of n-butyllithium in THF (4.6ml, 11.06mmol) was added to the mixture, after stirring at-78 ℃ for two hours, a solution of precursor 511 in tetrahydrofuran (2.63g, 10.05mmol) was added to the mixture and stirring was continued at-78 ℃ for 30 minutes, the mixture was stirred for about 16 hours after warming to room temperature, after the reaction was completed, a saturated ammonium chloride solution was added to the mixture and stirred at room temperature for about 20 minutes, the solvent was removed using a rotary evaporator, water/dichloromethane extraction was performed, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the resulting product was dissolved in a mixed solvent (concentrated sulfuric acid: glacial acetic acid ═ 2.5 ml: 45ml), after the mixture was stirred at 300 ℃ for about 7 hours, the mixture was cooled to room temperature and poured into ice methanol (150ml), the solid obtained by filtration was washed twice with ice methanol, the solid obtained was dissolved in methylene chloride, the solution was washed with water until the ph value was close to neutral, then dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to give 5213.12 g of a substantially pure precursor with a yield of 61%.¹H NMR(400MHz，CD₂Cl₂)：δ7.69-7.66(m，4H)，7.45(dd，J＝8.0，1.8Hz，2H)，7.38-7.32(m，2H)，7.27-7.22(m，3H)，7.06(dd，J＝6.6，1.8Hz，1H)，7.03-7.00(m，2H)，1.32(s，18H).¹³C NMR(125 MHz，CD₂Cl₂)：δ165.77，151.28，149.15，146.59，142.13，139.11，138.19，128.74，128.01，126.93，126.58，125.46，124.32，120.42，119.76，67.18，35.32，31.65.EI-MS：m/z 494.1468[M]+。

Among them, the precursor 511 can be prepared according to the following reaction formula and conventional reaction conditions.

Example 8 preparation of L5

Precursor 521(3.00g, 5.88mmol), 3, 5-diphenylphenylboronic acid (2.42g, 8.82mmol), and K were added to a reaction flask under nitrogen protection₂CO₃(2.44g，17.64mmol)、Pd(PPh₃)₄(0.68g, 0.59mmol) and a mixed solvent of water/toluene (volume ratio: 1: 8), the mixture was refluxed for 24 hours, the solvent was removed by a rotary evaporator, water/dichloromethane extraction was performed, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed by a rotary evaporator to obtain a crude product, and substantially pure l50.99g was obtained by a method of silica gel column chromatography (dichloromethane/n-hexane ═ 1: 5) with a yield of 65%.

¹H NMR(500MHz，CD₂Cl₂)：δ8.14(d，J＝1.5Hz，2H)，7.83(t，J＝2.0Hz，1H)，7.75(d，J＝8.0Hz，1H)，7.71(d，J＝8.0Hz，2H)，7.69-7.64(m，7H)，7.48(t，J＝7.5Hz，4H)，7.44(dd，J＝8.0，2.0Hz，2H)，7.40(tt，J＝7.0，1.5Hz，2H)，7.26-7.16(m，5H)，7.13(d，J＝7.5Hz，1H)，1.25(s，18H).¹³C NMR(125MHz，CD₂Cl₂)：δ164.65，156.57，151.00，150.38，146.90，142.47，141.40，140.99，138.38，137.53，129.20，128.44，128.42，127.92，127.71，126.86，126.61，125.18，125.03，124.18，120.83，119.68，118.75，68.00，35.23，31.67.EI-MS：m/z 659.3541[M]+.

In addition, according to the preparation concept and method of the ligand compound used in examples 1 to 9, the following ligand compounds can be prepared respectively, and are not described herein again.

Preparation of tetradentate gold (III) complex

As shown in the following formula, the tetradentate coordination gold (III) complex shown in the formula (0-I) can be prepared by performing C-H (carbon-hydrogen bond) activation and intramolecular Au-C (gold-carbon bond) coupling reaction on a precursor shown in the formula (0-II) under the microwave promotion, or can be prepared by performing intermolecular coordination coupling reaction on the precursor shown in the formula (0-III) and an Au (III) reagent under the microwave promotion based on C-H activation, and then performing intramolecular Au-C coupling reaction on an intermolecular coupling product under the microwave. The precursors 0-III can also be obtained by C-H activation reaction of Hg (II) reagent and metal replacement reaction with Au (III) reagent, and in addition, the coordination anions of the precursors of the formula (0-II) can be replaced by using a conventional replacement method.

When the parent nucleus of the tetradentate gold (III) complex has relatively large or sensitive substituents, e.g. NR¹⁷R¹⁸Or firstly preparing the tetradentate gold (III) complex with the same position substituted by halogen by using the microwave reaction method provided by the invention, taking the tetradentate gold (III) complex as a precursor, and converting the halogen group at the corresponding position into NR¹⁷R¹⁸Groups, i.e. complex or multiple tetradentate gold (III) complexes with a common substructure, can be obtained by derivatization reactions based on simple tetradentate gold (III) complexes as precursors. Therefore, the preparation method of the tetradentate gold (III) complex provided by the invention can realize rich and diverse tetradentate gold (III)And (3) constructing a coordination gold (III) complex.

Example 9-L1-Au (III) Cl

L1(2.00g, 3.46mmol) in combination with Hg (OAc)₂(1.43g, 4.50mmol) in 45mLEtOH was heated to reflux for 48 h, LiCl (0.73g, 17.30mmol) was added to the reaction mixture, heated to reflux for 2 h, cooled to room temperature, the solid collected by filtration, washed twice with ethanol and drained to give L1-HgCl (1.57g, 1.93mmol, 56% yield) as a white solid, directly with KAuCl₄(0.80g, 2.12mmol) was heated under reflux in 35mL acetonitrile for 48 h, after the reaction mixture was cooled, the resulting solid was collected by filtration, washed twice with acetonitrile and dried by suction to give L1-AuCl (0.84g, 1.04mmol) as a yellow solid in 54% yield.

The preparation method described in this example is reported in the documents K. -H.Wong, K. -K.Cheung, M.C. -W.Chan, C. -M.Che, Organometallics 1998, 17, 3505-3511, and the prepared L1-Au (III) Cl can be directly used in the next reaction without further purification.

Example 10-L1-Au (III) OCOCOCF₃

L1-Au (III) Cl (0.84g, 1.04mmol) and AgOCOCOCF₃(0.25g, 1.14mmol) in 45mL of dichloromethane and stirring in the dark for about 16 hours, after the reaction solution was filtered through celite, the filtrate was collected, the solvent was removed using a rotary evaporator and dried to give L1-Au (III) OCOCOCF₃And (5) crude product.

The preparation method of this example is reported in documents D. -A.Rosca, D.A.Smith, M.Bochmann, chem.Commun.2012, 48, 7247-₃The crude product was used directly in the next reaction without further purification.

EXAMPLE 11 preparation of Complex 1

In a 10mL microwave reaction tube, L1-Au (III) Cl (25mg, 0.03mmol) was dissolved in ACN/H₂O (v: v ═ 1: 1, ca. 3ml) mixed solvent the mixture was heated to 120 ℃ in a microwave reaction oven and kept at this temperature for 20min. After the reaction is finished, water is added into the system, the water phase is extracted for 2-3 times by dichloromethane, the organic phases are combined and dried by anhydrous magnesium sulfate, and the pure complex 1 product of 3.6mg is obtained by dichloromethane/normal hexane silica gel column chromatography, with the yield of 15%.

¹H NMR(500MHz，CD₂Cl₂)：δ8.48(dd，J＝7.5，1.5Hz，1H)，8.22(d，J＝2.0Hz，1H)，7.82-7.80(m，2H)，7.74(d，J＝9.0Hz，2H)，7.65(d，J＝1.5Hz，1H)，7.45-7.38(m，5H)，7.28(d，J＝2.0Hz，1H)，7.18-7.15(m，2H)，7.12(d，J＝8.0Hz，2H)，7.08(d，J＝9.0Hz，2H)，7.00(d，J＝2.5Hz，1H)，3.90(s，3H)，1.45(s，9H).¹³C NMR(125MHz，CD₂Cl₂)：δ170.29，163.99，162.25，161.71，158.40，157.94，154.32，154.21，151.41，151.28，149.96，149.62，136.45，134.70，132.35，130.49，130.26，129.29，128.52，126.22，124.06，123.99，122.78，119.45，118.44，116.87，115.25，115.10，114.81，112.16，109.48，35.97，31.74，30.30.ESI-MS：m/z 772.2111[M+H]⁺.Elemental analysis calculated for C₄₀H₃₂AuNO₃+0.5CH₂Cl₂：C，59.75；H，4.09；N，1.72；found：C，59.63；H，4.09；N，1.72.

EXAMPLE 12 preparation of Complex 1

In a 10ml microwave reaction tube, L1-Au (III) OCOCF₃(28mg, 0.032mmol) was dissolved in ACN/H₂O (v: v ═ 1: 1, 3.2ml) mixed solution, the mixture was heated to 120 ℃ in a microwave reaction chamber and kept at that temperature for 20min, water was added to the system after the reaction was completed, the aqueous phase was extracted with dichloromethane 2 to 3 times, the organic phases were combined and dried over anhydrous magnesium sulfate, and a dichloromethane/n-hexane silica gel column chromatography was used to obtain pure complex 1, 22.0mg, yield 90%.

EXAMPLE 13 preparation of Complex 2

Preparation of L1-Au (III) OCOCF with reference to examples 9 and 10₃The method of (1) prepares L2-Au (III) OCOCF₃. Then, in a 10ml microwave reaction tube, L2-Au (III) OCOCOCF₃(280mg, 0.282mmol) in ACN/H₂O (v: v ═ 1: 1, 16ml) mixed solution, the mixture was heated to 120 ℃ in a microwave reaction chamber and kept at that temperature for 20min, water was added to the system after the reaction ended, the aqueous phase was extracted 2-3 times with dichloromethane, the organic phases were combined and dried over anhydrous magnesium sulfate, concentrated, and purified complex 2 was obtained by chromatography using dichloromethane/n-hexane silica gel column: 220mg, a yield of 89%,

¹H NMR(500MHz，CD₂Cl₂)：δ8.29(dd，J＝7.5，1.5Hz，1H)，8.23(d，J＝2.0Hz，1H)，7.78(s，1H)，7.75(d，J＝8.5Hz，1H)，7.70(s，1H)，7.65(s，1H)，7.55(d，J＝1.5Hz，2H)，7.48(dd，J＝8.5，2.0Hz，1H)，7.42-7.37(m，4H)，7.32(d，J＝2.0Hz，1H)，7.19-7.11(m，4H)，6.96(d，J＝2.0Hz，1H)，1.42(s，18H).ESI-MS：m/z 876.1737[M+H]⁺.Elemental analysis calculated for C₄₃H₃₇AuBrNO₂：C，58.91；H，4.25；N，1.60；found：C，59.08；H，4.52；N，1.55.

for complex L2-Au (III) OCOCF₃，¹⁹F NMR(376MHz，CD₂Cl₂)：δ-73.16。

EXAMPLE 14 preparation of complexes 3 and 4

And (3) complex: complex 2(35mg, 0.04mmol) and Pd (dba)₂(9.2mg, 0.008mmol), Binap (5.0mg, 0.008mmol), KOtBu (13.4mg, 0.12mmol) in toluene were heated under reflux for 24 hours, after the reaction was cooled to room temperature, water was added to the system, the aqueous phase was extracted with dichloromethane 2-3 times, the organic phases were combined and dried over anhydrous magnesium sulfate, and column chromatography was performed using dichloromethane/n-hexane silica gel column to give pure complex 3: 17mg, yield 45%.

¹H NMR(500MHz，CD₂Cl₂)：δ7.83(dd，J＝8.0，2.0Hz，1H)，7.72-7.69(m，2H)，7.65(d，J＝1.5Hz，1H)，7.62(t，J＝2.0Hz，1H)，7.55-7.53(m，3H)，7.40-7.36(m，6H)，7.32(dd，J＝8.0，1.5Hz，1H)，7.29-7.24(m，6H)，7.20-7.13(m，3H)，7.11-7.09(m，2H)，6.96(dd，J＝8.0，2.0Hz，1H)，6.92(d，J＝2.0Hz，1H)，6.74-6.71(m，1H)，1.41(s，18H).¹³C NMR(125MHz，CD₂Cl₂)：δ171.38，163.57，161.41，158.31，157.60，156.04，152.48，151.45，151.07，150.44，149.61，147.57，144.18，138.07，135.72，134.14，130.29，129.89，128.18，127.39，127.35，126.41，124.81，124.50，123.93，122.41，122.00，119.25，118.34，118.06，116.45，115.78，114.87，112.04，109.00，35.44，31.62.ESI-MS：m/z 965.3333[M+H]⁺.Elemental analysis calculated for C₅₅H₄₇AuN₂O₂：C，68.46；H，4.91；N，2.90；found：C，68.46；H，4.91；N，2.85.

The complex 4: complex 2(90mg, 0.10mmol) and Pd (dba)₂(23.7mg，0.021mmol)，Binap(12.8mg，0.021mmol)，KO^tBu (33.7mg, 0.30mmol) in toluene is heated under reflux for 24 hours, after the reaction mass is cooled to room temperature, water is added to the system, the aqueous phase is extracted 2-3 times with dichloromethane, the organic phases are combined and dried with anhydrous magnesium sulfate, and the pure product is obtained by chromatography using dichloromethane/n-hexane silica gel columnIs a complex 4: 30mg, yield 40%.

¹H NMR(500MHz，CD₂Cl₂)：δ8.23(dd，J＝7.5，1.5Hz，1H)，8.05(d，J＝2.0Hz，1H)，8.01(d，J＝8.0Hz，1H)，7.79(s，1H)，7.67-7.65(m，2H)，7.58(d，J＝2.0Hz，2H)，7.40-7.27(m，6H)，7.16(t，J＝7.5Hz，1H)，7.07-7.02(m，3H)，6.86(d，J＝2.0Hz，1H)，6.70-6.60(m，6H)，6.16(dd，J＝8.0，1.5Hz，2H)，1.44(s，18H).¹³C NMR(125MHz，CD₂Cl₂)：δ173.98，162.69，161.56，158.61，157.23，156.62，152.63，152.08，151.08，150.81，149.28，144.44，141.09，137.85，137.17，135.86，134.78，132.66，130.36，128.75，128.69，128.53，125.07，124.19，123.74，122.89，122.14，121.66，119.53，118.15，117.03，116.54，115.71，115.69，113.88，112.19，108.91，35.50，31.65.ESI-MS：m/z 978.3072[M]⁺.Elemental analysis calculated for C₅₅H₄₅AuN₂O₃+MeOH：C，66.53；H，4.89；N，2.77；found：C，66.77；H，4.68；N，2.84.

It is to be noted that the following complexes with other, different N substituents can also be prepared in the same manner as described above for example 14 starting from complex 2

EXAMPLE 15 preparation of Complex 5

Preparation of L1-Au (III) OCOCF with reference to examples 9 and 10₃The method of (1) prepares L3-Au (III) OCOCF₃. In a 10ml microwave reaction tube, L3-Au (III) OCOCF₃(27mg, 0.042mmol) in ACN/H₂O (v: v ═ 1: 1, total 3mL) mixed solvent the mixture was heated to 120 ℃ in a microwave reaction chamber and the mixture was maintainedAfter the reaction is finished at the temperature of 20min, when the mixture is cooled to room temperature, adding water into the system, extracting the water phase for 2-3 times by using dichloromethane, combining organic phases, drying by using anhydrous magnesium sulfate, removing the solvent by using a rotary evaporator, and finally performing chromatography by using dichloromethane/n-hexane silica gel column to obtain a pure complex 5: 20mg, yield 90% with respect to L3.

¹H NMR(500MHz，CD₂Cl₂)：δ8.35(dd，J＝7.5，1.5Hz，1H)，8.06(d，J＝7.0Hz，1H)，7.83(t，J＝8.0Hz，1H)，7.75(d，J＝8.0Hz，1H)，7.71(d，J＝7.0Hz，1H)，7.59(d，J＝8.0Hz，1H)，7.49(td，J＝7.0，1.0Hz，1H)，7.43-7.36(m，2H)，7.30(td，J＝7.5，1.0Hz，1H)，7.21(d，J＝8.0Hz，1H)，7.14-7.11(m，1H)，7.08(d，J＝8.0Hz，1H)，2.64(s，3H).¹³C NMR(100MHz，CDCl₃)：δ171.02，164.55，163.06，152.05，149.55，148.42，148.32，141.58，140.04，136.50，135.21，133.51，132.80，131.10，128.39，126.77，126.33，122.38，121.40，118.93，117.87，117.58，117.26，22.91.EI-MS：m/z 531.0901[M]⁺.Elemental analysis calculated for C₂₄H₁₆AuNO：C，54.25；H，3.04；N，2.64；found：C，54.14；H，2.87；N，2.66.

EXAMPLE 16 preparation of Complex 5

In a 10mL microwave reaction tube, L3 ligand (28mg, 0.08mmol), Au (OAc)₃(0.03g, 0.09mmol) and sodium trifluoroacetate (0.05g, 0.36mmol) in acetic acid/H₂Mixing O (v: v ═ 1: 1, total 3mL) solvent, heating to 150 ℃ in a microwave reactor and keeping the temperature for reaction for 30min, after the reaction is finished, cooling the mixture to room temperature, adding water into the system, extracting the water phase with dichloromethane for 2-3 times, combining the organic phases, washing with water for 2-3 times until the pH of the water phase is about 7, drying the organic phase with anhydrous magnesium sulfate, concentrating under reduced pressure to remove the solvent to obtain crude product, and directly dissolving the crude product in ACN/H₂Heating to 140 deg.C in a microwave reactor in a mixed solvent of O (v: v ═ 1: 1, total 10ml) and maintaining the temperature for 70 minutes, after the reaction is finished, cooling the mixture to room temperature, adding water to the system, and adding the water phaseThe extraction is carried out 2-3 times with dichloromethane, the organic phase is dried over anhydrous magnesium sulphate, the organic solvent is removed by a rotary evaporator, and finally the column chromatography is carried out by dichloromethane/n-hexane silica gel column to obtain 14mg of pure product with 33 percent yield.

EXAMPLE 17 preparation of Complex 6

Preparation of L1-Au (III) OCOCF with reference to examples 9 and 10₃The method of (1) prepares L4-Au (III) OCOCF₃. In a 10ml microwave reaction tube, L4-Au (III) OCOCF₃(20mg, 0.028mmol) in ACN/H₂O (v: v ═ 1: 1, ca. 2ml) in a mixed solvent. The mixture was heated to 115 ℃ in a microwave reaction chamber and kept at this temperature for 20min. After the reaction was completed, after the mixture was cooled to room temperature, water was added to the system, and the aqueous phase was extracted with dichloromethane 2 to 3 times. The combined organic phases are dried over anhydrous magnesium sulphate and the solvent is removed using a rotary evaporator, and finally a column chromatography is carried out using dichloromethane/n-hexane silica gel to give the pure product: the complex 6: 16mg, yield 92%.

¹H NMR(500MHz，CD₂Cl₂)：δ8.22(dd，J＝8.0，2.0Hz，1H)，8.00(d，J＝7.0Hz，1H)，7.92(td，J＝8.0，2.5Hz，1H)，7.83(dd，J＝8.5，3.0Hz，1H)，7.76(d，J＝7.5Hz，1H)，7.66(dd，J＝8.0，2.5Hz，1H)，7.57(s，1H)，7.51(t，J＝7.0Hz，1H)，7.33(t，J＝7.5Hz，1H)，7.24-7.22(m，2H)，7.14(d，J＝8.5Hz，1H)，2.70(s，3H).ESI-MS：m/z 610.0039[M+H]⁺.Elemental analysis calculated for C₂₄H₁₅AuBrNO+H₂O：C，45.88；H，2.73；N，2.23；found：C，46.24；H，2.56；N，2.28.

For complex L4-Au (III) OCOCF₃，¹⁹F NMR(376MHz，CD₂Cl₂)：δ-73.07.

EXAMPLE 18 preparation of complexes 7 and 8

The preparation process of the complex 7 comprises the following steps: after complex 1(90mg, 0.15mmol) and diphenylamine (76.2mg, 0.45mmol), Pd (dba)2(17.3mg, 0.03mmol), Binap (37.4mg, 0.06mmol), KOtBu (50.5mg, 0.45mmol) were heated under reflux in toluene (35ml) for 24 hours, after the reaction was cooled to room temperature, water was added to the system, the aqueous phase was extracted 2-3 times with dichloromethane, the combined organic phases were dried over anhydrous magnesium sulfate and column chromatography was performed using dichloromethane/n-hexane silica gel to give pure product: the complex 7: 44mg, yield 43%.¹H NMR(500MHz，CD₂Cl₂)：δ8.25(d，J＝8.0Hz，1H)，8.07(d，J＝7.5Hz，1H)，7.94(t，J＝8.0Hz，1H)，7.87(d，J＝8.0Hz，1H)，7.78(d，J＝7.5Hz，1H)，7.70(d，J＝8.0Hz，1H)，7.49(t，J＝7.5Hz，1H)，7.33-7.28(m，5H)，7.17(d，J＝7.0Hz，5H)，7.13(d，J＝8.5Hz，1H)，7.10(d，J＝2.5Hz，1H)，7.06(t，J＝7.5Hz，2H)，6.86(dd，J＝8.5，2.5Hz，1H)，2.72(s，3H).ESI-MS：m/z 699.1661[M+H]⁺.Elemental analysis calculated for C₃₆H₂₅AuN₂O：C，61.90；H，3.61；N，4.01；found：C，61.71；H，3.61；N，4.10.

The preparation process of the complex 8 comprises the following steps: complex 6(150mg, 0.25mmol) and phenoxazine (137.4mg, 0.75mmol), Pd (dba)2(14.4mg, 0.025mmol), Binap (31.1mg, 0.05mmol), KO^tAfter Bu (84.2mg, 0.75mmol) was heated under reflux in toluene for 24 hours, after the reaction was cooled to room temperature, water was added to the system, the aqueous phase was extracted with dichloromethane 2-3 times, the organic phases were combined and dried over anhydrous magnesium sulfate, and column chromatography was performed using dichloromethane/n-hexane silica gel to give the pure product: the complex 8: 82mg, yield 47%.

¹H NMR(500MHz，CD₂Cl₂)：δ8.61(d，J＝8.0Hz，1H)，8.13(dd，J＝7.0，1.0Hz，1H)，7.97(t，J＝8.0Hz，1H)，7.90(d，J＝8.0Hz，1H)，7.81(dd，J＝8.0，1.0Hz，1H)，7.73(d，J＝7.5Hz，1H)，7.55(td，J＝7.0，1.0Hz，1H)，7.42(d，J＝2.5Hz，1H)，7.36(td，J＝7.5，1.0Hz，1H)，7.29(d，J＝8.5Hz，1H)，7.19(d，J＝8.5Hz，1H)，7.10(dd，J＝8.0，2.5Hz，1H)，6.70-6.60(m，6H)，6.11(dd，J＝7.5，2.0Hz，2H)，2.75(s，3H).ESI-MS：m/z 712.1395[M]⁺.Elemental analysis calculated for C₃₆H₂₃AuN₂O₂+H₂O：C，59.19；H，3.45；N，3.83；found：C，59.18；H，3.27；N，3.92.

It is to be noted that other complexes having different N-substituent substitutions shown below can also be prepared starting from complex 6 by the same or similar process as described in example 18 above.

Likewise, starting from ligand compounds having the same or similar skeletons and having different substituent substitutions, and with reference to the preparation and derivatization methods of the gold (III) complexes referred to in examples 9 to 18, it is also possible to prepare more abundant tetradentate gold (III) complexes

EXAMPLE 19 preparation of Complex 9

In a 35mL microwave reaction tube, L5 ligand (35mg, 0.05mmol) was reacted with Au (OAc)₃(0.02g, 0.06mmol) in a mixed solvent TFA/H₂Heating to 130 deg.C in O (v: v ═ 1: 1, total 12ml) in a microwave reactor and holding the temperature for 30min, after the reaction is finished, cooling the mixture to room temperature, addingAdding water into the system, extracting the water phase with dichloromethane for 2-3 times, combining the organic phases, washing with water for 2-3 times until the pH value of the water phase is about 7, drying the organic phase with anhydrous magnesium sulfate, removing the organic solvent by using a rotary evaporator, draining the obtained crude product, and dissolving the obtained solid in ACN/H without further purification₂Heating to 140 ℃ in a microwave reactor in a mixed solvent of O (v: v is 1: 1, and the total volume is 12ml), keeping the temperature for 80 minutes, after the reaction is finished, cooling the mixture to room temperature, adding water into the system, extracting 2-3 times by dichloromethane, drying an organic phase by anhydrous magnesium sulfate, removing the organic solvent by using a rotary evaporator, and finally performing column chromatography by using dichloromethane/n-hexane silica gel to obtain a pure product complex 9: 24mg, yield 32%.

¹H NMR(500MHz，CD₂Cl₂)：δ8.29(d，J＝7.0Hz，1H)，8.06(s，2H)，7.93(d，J＝7.5Hz，1H)，7.83(d，J＝8.0Hz，1H)，7.76(s，1H)，7.72-7.68(m，6H)，7.65(d，J＝7.5Hz，1H)，7.51(t，J＝7.5Hz，2H)，7.46(dd，J＝8.0，1.5Hz，2H)，7.40(t，。J＝7.5Hz，1H)，7.33(t，J＝7.5Hz，1H)，7.25-7.22(m，2H)，7.01-6.97(m，2H)，6.93-6.89(m，1H)，1.25(s，18H).¹³C NMR(125MHz，CD₂Cl₂)：δ181.80，169.29，166.53，162.47，158.63，152.28，151.71，149.77，148.35，143.99，143.25，142.35，141.72，141.55，138.65，138.14，135.12，129.25，128.21，127.80，127.71，127.34，126.74，126.06，125.66，124.81，122.88，122.79，122.02，121.39，120.30，119.59，75.37，35.46，31.60.ESI-MS：m/z 854.3043[M+H]⁺.Elemental analysis calculated for C₅₀H₄₂AuN：C，70.33；H，4.96；N，1.64；found：C，70.25；H，5.27；N，1.64.

EXAMPLE 20 preparation of Complex 9

In a 35mL microwave reaction tube, L5 ligand (35mg, 0.05mmol) was reacted with Au (OAc)₃(0.02g, 0.06mmol) and sodium trifluoroacetate (0.04g, 0.29mmol) in a mixed solvent of AcOH/H₂O (v: v 2: 1, total 12ml) inHeating to 170 deg.C in microwave reactor and maintaining the temperature for 25min, cooling the mixture to room temperature after the reaction is finished, adding water into the system, extracting the water phase with dichloromethane for 2-3 times, combining the organic phases, washing with water for 2-3 times until the pH value of the water phase is about 7, drying the organic phase with anhydrous magnesium sulfate, removing the organic solvent with rotary evaporator, and draining the obtained crude product to obtain solid which can be directly dissolved in ACN/H without further purification₂Heating to 130 ℃ in a microwave reactor in a mixed solvent of O (v: v ═ 1: 2, which is 12ml in total), keeping the temperature for 80 minutes, after the reaction is finished, cooling the mixture to room temperature, adding water into the system, extracting 2-3 times by dichloromethane, drying an organic phase by anhydrous magnesium sulfate, removing the organic solvent by using a rotary evaporator, and finally performing column chromatography by using dichloromethane/n-hexane silica gel to obtain a pure product complex 9: 29mg, yield 39%.

Likewise, from the preparation and derivatization of gold (III) complexes involved in the combination of ligands having the same or similar backbones and having different substituent substitutions, it is also possible to prepare an abundance of tetradentate gold (III) complexes having the same backbone structure, as shown below:

example 21 photophysical Properties of complexes 1-8

Measurement of ultraviolet and visible absorption spectra: dissolving the complex in a solvent (solution concentration of 2X 10)^-5mol/L), the solution of the specified concentration was deoxygenated and the absorbance spectrum of the complex was measured at room temperature using a machine "Hewlett-Packard 8453 diode array spectrophotometer". Measurement of emission spectra: luminescence spectra 1) -3) were measured using the instrument "Horiba Fluorolog-3 spectrophotometer". 1) Dissolving the complex in a solvent (solution concentration of 2X 10)^-5mol/L), deoxidizing the solution with specific concentration, and measuring the emission spectrum of the complex solution (solution state) at room temperature. 2) The solid of the complexThe solid state emission spectrum of the complex was measured by placing it in a quartz tube having an inner diameter of 4mm under conditions of room temperature and 77K (liquid nitrogen), respectively. 3) A very small amount of the complex was dissolved in a mixed solvent (ethanol/methanol/dichloromethane ratio 4: 1, solvent volume ratio), the prepared solution was charged into a quartz tube having an inner diameter of 4mm, and the glassy state emission spectrum of the complex was measured under 77K (liquid nitrogen). 4) The complex and PMMA were dissolved in chlorobenzene to obtain a clear solution with a mass fraction of 4 wt% of the complex, 50L of the solution was dropped on a quartz plate having a size of 1cm × 1cm × 0.1cm, and the plate was dried at 80 ℃ to obtain a clear quartz plate carrying the complex and PMMA, which was measured at room temperature using an instrument "Hamamatsu C11347 Quantaurus-QY Absolute PL quantum yield systems".

Measurement of luminescence lifetime: all luminescence lifetimes were measured in the instrument "Quanta Ray GCR 150-10 pulsed Nd: YAG laser system "was used.

The results are shown in FIGS. 2-8, FIG. 2 showing that the solution solubility of (a) complexes 1 and 2 and (b) complexes 5 and 6 in deoxygenated toluene (Au (III) complex is 2X 10 at room temperature in one embodiment of the present invention^-5mol/L) absorption spectrum; FIG. 3 shows, in one embodiment of the present invention, (a) Complex 3, (b) Complex 4, (c) Complex 7, and (d) Complex 8 in different deoxygenated solvents at room temperature (solution solubility of gold (III) Complex 2X 10)^-5mol/L) absorption spectrum; FIG. 4 shows that, in one embodiment of the present invention, the solution solubility of (a) complex 1-4 and (b) complex 5-8 in deoxygenated toluene (Au (III) complex is 2X 10 at room temperature^-5mol/L) emission spectra of (c) complex 4 at 2X 10 at room temperature^-5Emission spectra in deoxygenated/oxygenated toluene at mol/L concentration (asterisk "-" indicates 2-step transition at 380nm excitation wavelength); FIG. 5 shows that, in one embodiment of the present invention, the solution solubility of (a) complex 3, (b) complex 4, (c) complex 7 and (d) complex 8 in different deoxygenated solvents (Au (III) complex is 2X 10 at room temperature^-5mol/L) emission spectrum; FIG. 6 shows that, in one embodiment of the present invention, (a) complexes 1-4 and (b) complexes 5-8 are at PM at room temperatureEmission spectrum of MA film (mass fraction of Au (III) complex in film is 4%); FIG. 7 shows that in one embodiment of the present invention, complex 9 has a solution solubility of 2X 10 in deoxygenated dichloromethane (gold (III) complex at room temperature^-5mol/L), an absorption spectrum (a) and an emission spectrum (b), an emission spectrum (c) of the complex 9 in a PMMA thin film (mass fraction of Au (III) complex in the thin film is 4%) at room temperature; FIG. 8 shows a TGA profile of each complex in an embodiment of the present invention, wherein (a) complex 3 loses 2% weight at 394 deg.C; (b) the weight loss of the complex 4 is 2 percent when the temperature is raised to 429 ℃; as can be seen from FIGS. 2 and 3, in toluene, the complexes 1 to 8 showed strong absorption [ ε ═ 1-4. times.10 at an absorption peak of 300-330nm⁴dm³mol^-1cm^-1]And exhibits moderate absorption intensity [ epsilon ═ 5-29). times.10 at an absorption peak of 380-400nm³dm³mol^-1dm^-1]. It was also observed in complexes 3, 4, 7 and 8 that at 420-500nm there were broad and weak absorption bands from intracigand charge transfer transitions of π (diphenylamine or phenoxazine) - π (C ^ C ^ N C ligands) (C ^ C ligands)¹ILCT).

As can be seen from FIG. 3, when the absorption of complexes 3, 4, 7 and 8 is studied along with the change of the solvent, it can be seen that the absorption spectrum of each complex is less sensitive to the polarity of the solvent, the shift of the absorption peak is almost unchanged, but the intensity of the absorption peak is slightly changed.

As can be seen from fig. 4, complexes 1-8 exhibit three different types of light emitting properties: on the one hand, the complexes 1-2 and 5-6 both show vibrational emission bands with quantum yields up to 54% and luminescence lifetimes up to 225 μ s_r) Smaller, in the range of 1.2X 10³To 5.8X 10³s^-1Thus, based on the principle of the presence of large Stokes shifts, characteristic emission spectral bands with vibrating structures, and small radiation attenuation rate constants kr, the emitted light of 1-2 and 5-6 should be four-toothed with metal perturbations C ^ C ^ N ^ C]Phosphorescence resulting from pi-pi transition within the ligand; on the other hand, complexes 2, 3, 4 and complexes 5, 6 and 7, 8 have similar cyclometalated ligand structuresBut shows completely different luminescence properties, the complexes 3, 4, 7 and 8 show a broad band with a non-fine structure and have a larger radiation attenuation rate constant kr in comparison, which means that the original luminescence mechanism is changed after N-substituent groups are introduced into the ring metal ligand structures of 3, 4, 7 and 8; among them, complex 3 observed a red shift of luminescence from 550nm in toluene solvent to 570nm in o-xylene solvent, i.e. the wavelength of the emitted light changes with the polarity of the solvent, which indicates the presence of charge transfer characteristic of the excited state, combined with its emission spectrum of non-fine structure, longer luminescence lifetime (relative to that of 4, 7, 8) and moderate radiative decay rate constant k_rValue, luminescence of Complex 3 corresponds to³Charge transfer in ILCT triplet complexes [ pi (diphenylamine structure) to pi x (C ^ C ^ N ^ C)]A light emitting feature. Taking complex 4 as an example, if the solvent is replaced by deoxidized o-xylene from toluene, the strongest emitted light is red-shifted by 66nm, which means that the light-emitting excited state of complex 4 also has the characteristic of charge transfer, and by simultaneously studying the light emission of complex 4 in the deoxidized toluene and the oxygen-containing toluene, as shown in (c) of fig. 4, the light emission intensity in the deoxidized toluene is much lower than that in the deoxidized toluene, which indicates that the triplet excited state of complex 4 is involved in the light emission mechanism. The above luminescence phenomena combine its non-fine structured luminescence bands, short luminescence lifetime (< 1 mus) and large radiative decay rate constant k_rFully meets the thermal delayed fluorescence TADF luminescence characteristics based on thermodynamic activation, namely is perturbed by metal¹Charge transfer in ILCT singlet ligands [ pi (N-substituents) to pi ^ C (C ^ C ^ N ^ C ligands)]And (4) emitting light.

Therefore, it is fully demonstrated that the N-substituent-containing tetradentate gold (III) complex provided by the present invention generally has a short radiation decay life, and shows an ILCT characteristic or a TADF characteristic of charge transfer luminescence in a ligand.

1) The results of measuring the UV-visible absorption spectrum and emission spectrum data of the complexes 1 to 8 at room temperature are shown in the following Table 1:

TABLE 1

[a]The concentration of complexes 1-8 in deoxygenated toluene was 2X 10^-5Epsilon, [ b ] measured at mol/L]The complexes 1-8 are measured in deoxytoluene (the concentration is 2 x 10) by adopting a Hamamatsu C11347 Quantaurus-QY Absolute PL photoluminescence Absolute quantum yield measuring system^-5mol/L) of the luminescence quantum yield (. PHI.); τ is the luminescence lifetime; k is a radical of_rIs the radiation decay rate constant. [ c ] is]The luminescence quantum yield of PMMA film samples (containing 4 wt% of tetradentate Au (III) complex) was measured using a Hamamatsu C11347 Quantaurus-QY Absolute PL photoluminescence Absolute quantum yield measurement system.

2) The concentration of complex 9 in deoxygenated dichloromethane was determined to be 2X 10^-5Absorption wavelength at mol/L and optical absorption coefficient (. epsilon.. times.10) at the corresponding wavelength³mol^-1dm³cm^-1]) 269(57.08), 282(50.48), 304(22.33), 335(9.24), 359(4.99), 389(2.52), respectively, the concentration of complex 9 in deoxygenated dichloromethane being 2X 10^-5The luminescence wavelength at mol/L is mainly 483, 515 and 555 nm.

3) The results of emission spectra (solvent effect) of complexes 3, 4, 7, 8 in different solvents are shown in fig. 5, wherein the data for complexes 3 and 4 are shown in table 2 below

TABLE 2

Data for complexes 7 and 8 are shown in Table 3 below

TABLE 3

Example 22 general procedure for device preparation

a) Adopting a pre-patterned ITO transparent glass substrate, carrying out ultrasonic cleaning and deionized water rinsing by using a detergent, then sequentially cleaning in an ultrasonic bath of deionized water, acetone and isopropanol, and drying for later use;

b) transferring the dried substrate into a vacuum chamber, sequentially depositing through thermal evaporation to obtain a plurality of functional layers with preset thickness in the OLED,

c) finally, LiF and Al (cathode) are deposited on the electron transport layer film in sequence by vacuum thermal evaporation.

The measurement conditions of the parameters are as follows:

the thickness of each material layer deposited by vacuum was monitored in situ using a quartz oscillator film thickness gauge. EL spectrum, brightness, color Coordinates (CIE), electroluminescence efficiency were measured by Photo Research Inc PR-655 or Hamamatsu photosynergic absolute quantum efficiency test system (Hamamatsu phosphor absolute quantitative outside quality measurement system) type C9920-12. The voltage-current characteristics were measured using a Keithley 2400 power cell. All devices were characterized in an unpackaged condition in an atmospheric environment.

Example 23 Complex 4 as an OLED emitting dopant

The complex 4 is adopted as a dopant, the doping concentrations are set to be 4 wt%, 8 wt% and 16 wt%, and the OLED device structure sequentially comprises the following components from an anode to a cathode: ITO/HAT-CN (5nm)/TAPC (50 nm)/TCTA: complex 4 (doping concentration, 10nm)/TmPyPb (50nm)/LiF (1.2nm)/Al (100nm), and the corresponding OLED device was fabricated and obtained according to the general fabrication method and preset structural component parameters provided in example 22, and the specific process included:

a) adopting a pre-patterned ITO transparent glass substrate, carrying out ultrasonic cleaning and deionized water rinsing by using a detergent, then sequentially cleaning in an ultrasonic bath of deionized water, acetone and isopropanol, and drying for later use;

b) transferring the dried substrate into a vacuum chamber, and sequentially obtaining functional layers with preset thicknesses in the OLED through thermal evaporation and deposition, wherein the method comprises the following steps: HAT-CN (hole injection layer) 5nm thick, TAPC (hole transport layer HTL) 50nm thick, TCTA (light emitting layer EML) 10nm thick doped with 4 wt%, 8 wt% and 16 wt% of complex 4, respectively, TmPyPb (electron transport layer ETL) 50nm thick;

c) and finally, sequentially carrying out vacuum thermal evaporation and deposition on the LiF (electron injection layer) with the thickness of 1.2nm and the Al (cathode) with the thickness of 100nm on the electron transport layer film to obtain the OLED device.

Note that the doping concentration is guest material mass/(guest material mass + host material mass) × 100%, and the host material have equivalent meanings herein, and the meanings of the OLED device and the OLED device are interchangeable herein.

Finally, the OLED device was subjected to voltage-current characteristics, EL spectrum, brightness, efficiency and color Coordinates (CIE) tests to obtain emission performance data as shown in table 4 below, see fig. 9.

TABLE 4 data for electroluminescent properties of OLED devices made with Complex 4 as dopant

[a]The maximum light-emitting brightness; [ b ] a]Current efficiency; [ c ] is]Power efficiency; [ d]External quantum efficiency; [ e ] a]Emission luminance 1000cd m^-2CIE coordinates of time; CIE refers to color coordinates.

As can be seen from Table 4, all three devices exhibited green emission, 70-80cd A^-1Maximum current efficiency of 25%, maximum external quantum efficiency of 25%, and luminance of 1000cd m^-2The external quantum efficiency is up to 22%, the efficiency is reduced to 12.1%, the improvement of the doping concentration in a certain range (4-8%) has obvious influence on the maximum luminous brightness, the current efficiency, the external quantum efficiency and the efficiency roll-off, the improvement is continued to 16%, and the change is small.

Example 24-Complex 7 as an OLED luminescent dopant (investigation of doping concentration)

The complex 7 is used as a dopant, the doping concentrations are respectively set to be 2 wt%, 4 wt% and 6 wt%, and the OLED structure comprises the following components in sequence from an anode to a cathode: ITO/HAT-CN (5nm)/TAPC (40 nm)/TCTA: complex 7(20nm)/TmPyPb (50nm)/LiF (1.2nm)/Al (100nm), the corresponding OLED device was fabricated and obtained according to the general fabrication method and preset structural component parameters of example 22 with reference to example 23, and finally, voltage-current characteristics, EL spectrum, efficiency and color coordinate tests were performed thereon to obtain light emitting property data as shown in table 5 below, see fig. 10.

TABLE 5 data for electroluminescent properties of OLED devices made with Complex 7 as dopant

[a]The maximum light-emitting brightness; [ b ] a]Current efficiency; [ c ] is]Power efficiency; [ d]External quantum efficiency; [ e ] a]Emission luminance 1000cd m^-2CIE coordinates of time; CIE color coordinates

As can be seen from Table 5, all three devices given show high luminance blue-green emission, 56-70cd A^-1The maximum current efficiency, the maximum external quantum efficiency of 23 percent can be obtained under the lower doping concentration, the influence of the continued improvement of the doping concentration on EQE, PE and CE is not obvious, and the maximum external quantum efficiency is 1000cd m^-2The external quantum efficiency under each doping concentration can be maintained between 12% and 16%.

Example 25-Complex 7 as an OLED emitting dopant (HTL/composite host/doping concentration)

In this embodiment, each OLED structure is characterized in that the light emitting layer EML adopts a host material compounded by TCTA and TPBi, the complex 7 is used as a guest material (dopant), the doping concentrations are set to 6 wt% and 10 wt%, and the OLED device structure sequentially includes, from the anode to the cathode: ITO/HAT-CN (5nm)/TAPC (40nm)/TCTA (10 nm)/TCTA: TPBi: complex 7(20nm)/TPBi (10nm)/TmPyPb (40nm)/LiF (1.2nm)/Al (100nm), the corresponding OLED device was manufactured and obtained according to the general preparation method and preset structural component parameters of example 22 with reference to example 23, and finally, voltage-current characteristics, EL spectrum, efficiency and color coordinate tests were performed thereon to obtain the emission performance data as shown in table 6 below, see fig. 11.

TABLE 6 data on the electroluminescent properties of OLED devices made with Complex 7 as dopant

[a]The maximum light-emitting brightness; [ b ] a]Current efficiency; [ c ] is]Power efficiency; [ d]External quantum efficiency; [ e ] a]Emission luminance 1000cdm^-2CIE coordinates of time; CIE color coordinates

Each OLED device in Table 6 showed high-luminance green emission, and 62-64cd A was obtained^-1And a maximum external quantum efficiency of up to 22%, at 1000cd m^-2The lower external quantum efficiency can be kept above 15%.

Example 27 Complex 8 as an OLED emissive dopant

The complex 8 is used as a dopant, the doping concentration is set to be 4 wt%, and the OLED device structure is set to be as follows from the anode to the cathode in sequence: ITO/HAT-CN (5nm)/TAPC (40nm)/TCTA (10 nm)/host material: complex 8(4 wt%, 10nm)/ETL (10nm)/TmPyPb (40nm)/LiF (1.2nm)/Al (100nm), the corresponding OLED device was manufactured and obtained according to the general preparation method and preset structural component parameters of example 22 with reference to example 23, and finally, voltage-current characteristics, EL spectrum, luminance and international color Code (CIE) test were performed thereon to obtain the emission performance data as shown in table 7 below, referring to fig. 12.

TABLE 7 data for electroluminescent properties of OLED devices made with Complex 8 as dopant

[a]The maximum light-emitting brightness; [ b ] a]Current efficiency; [ c ] is]Power efficiency; [ d]External quantum efficiency; [ e ] a]Emission luminance 1000cd m^-2CIE coordinates of time; CIE refers to color coordinates.

In Table 7, each OLED device showed high-brightness yellow-green luminescence, and at 4% doping concentration, the luminescent layer was designed as a single host material (No. 1) and a composite host material (Nos. 2 and 3), respectively, and 40-63cd A was obtained^-1Maximum current efficiency of 20%, maximum external quantum efficiency of 1000cd m^-2The external quantum efficiency can still be kept as high as 14%, which shows that different main body materials and structural designs have weak influence on the external quantum efficiency.

Example 28 stability testing

And (3) testing thermal stability: taking complexes 3 and 4, setting test conditions: the TGA profile was determined using the instrument "TGA Q50" from an initial temperature of 40 ℃ to 800 ℃ at a heating rate of 10 ℃ per minute, and is shown in fig. 8, wherein (a) is the TGA profile of complex 3 showing a weight loss of 2% at 394 ℃; (b) the TGA plot for complex 4, showing a 2% weight loss at 429 ℃, demonstrates that complexes 3 and 4 have excellent thermal stability and are able to withstand higher temperatures.

When the OLED is operated by a long-term current, the luminescent material is often deteriorated and decomposed due to heat generation and other reasons, and the operation life of the device is further affected. The above results fully indicate that the luminescent material obtained by the rigid tetradentate ligand chelate and the central metal has better thermal stability and material hardness, and has excellent heat and moisture resistance even under poor or limited conditions, which is very important for improving the device operation life (operation lifetime) of the OLED.

In summary, experiments prove that the complexes 1-8 have good luminescence characteristics, such as photoluminescence quantum yield, luminescence lifetime and radiation decay lifetime, and particularly the complexes 3, 4, 7 and 8 show that³ILCT luminescence signature and thermally induced delayed fluorescence TADF luminescence signature. The OLED luminescent device prepared by the complexes serving as luminescent materials or dopants shows blue-green to yellow-green luminescence, has high luminescence brightness, electroluminescent efficiency and maximum external quantum efficiency, and the maximum current efficiency is up to 78cd A by measurement^-1The external quantum efficiency is generally over 20 percent and can reach 25 percent at most, the EQE can still keep over 11 percent and can reach 22 percent at 1000 brightness value, and the efficiency is reduced to 11 percent; TGA thermal stability experiments prove that the complex can stably exist in air and humid environments, and has great development potential in the market of novel OLED luminescent materials.

However, according to the prior art, the currently known gold (III) complex emits mainly phosphorescence, and the emission efficiency is generally low, and the maximum value of EQE obtained is 21.6%, (nat. pho)tonics 2019, 13, 185-containing 191), which is different from the quadridentate coordination metal (III) thermotropic delayed fluorescence complex provided by the invention in the light-emitting principle, the ligand structure and the formed complex parent nucleus structure are different, and the OLED device obtained by the quadridentate coordination metal (III) thermotropic delayed fluorescence complex provided by the invention has better effect (EQE is up to 25.03%), and the light-emitting brightness is 1000cd m^-2In the meantime, the EQE can still be kept at 22.01%, the universality is good, and the tetradentate coordination gold (III) complex with different substituent groups and different substitution positions can achieve or basically achieve equivalent light-emitting performance meeting the commercial application requirements, so that the EQE is the best effect obtained in the OLED device using the gold (III) complex at present. Therefore, the tetradentate coordination gold (III) complex provided by the invention has outstanding advantages when being used as a luminescent material or a dopant for OLED.

All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention, are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. Unless otherwise indicated, all exact values provided herein are representative of corresponding approximate values (e.g., all exemplary exact values provided in accordance with particular factors or measurements can be considered to be corresponding approximate measurements also "about" modified, if desired).

The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any element as essential to the practice of the invention unless explicitly described as such.

Any aspect or embodiment of the invention described using terms such as "comprising," "having," "including," or "containing," when referring to an element, is intended herein to provide support for a similar aspect or embodiment of the invention that is "consisting of," consists essentially of, or "substantially comprises" the particular element, unless otherwise indicated or clearly contradicted by context (e.g., a composition described herein, when comprising the particular element, should be understood as also describing a composition consisting of that element, unless otherwise indicated or clearly contradicted by context).

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.