Metal complex containing adamantane structure, preparation method thereof and photoelectric device
阅读说明：本技术 一种含金刚烷结构的金属配合物及其制备方法和光电器件 (Metal complex containing adamantane structure, preparation method thereof and photoelectric device ) 是由 王辉 陈剑锋 李明 李建行 朱新财 刘志远 马晓宇 于 2020-07-09 设计创作，主要内容包括：本发明公开了一种含金刚烷结构的金属配合物及其制备方法和光电器件,属于发光材料技术领域,其结构通式为：M(L<Sub>A</Sub>)<Sub>a</Sub>(L<Sub>B</Sub>)<Sub>b</Sub>(L<Sub>C</Sub>)<Sub>c</Sub>；式中,配位体L<Sub>A</Sub>的结构通式为：<Image he="393" wi="334" file="DDA0002577958160000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>配位体L<Sub>B</Sub>的结构通式为：<Image he="280" wi="278" file="DDA0002577958160000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>配位体L<Sub>C</Sub>的结构通式为：<Image he="446" wi="425" file="DDA0002577958160000013.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>M为具有大于40的原子数的金属；a、b、c均为自然数,且a、b、c的总和为M的氧化数；Ar<Sub>1</Sub>为金刚烷基且x+y≥1；Z为氧或硫。本发明提供的金属配合物,其配体中含有金刚烷结构,将该金属配合物作为光电器件的发光层掺杂材料,不仅可以使光电器件的发光效率以及使用寿命得到提高,而且还可以降低光电器件的驱动电压。(The invention discloses a metal complex containing a adamantane structure, a preparation method thereof and a photoelectric device, belonging to the technical field of luminescent materials and having a structural general formula as follows: m (L) A ) a (L B ) b (L C ) c (ii) a In the formula, a ligand L A The general structural formula is as follows: ligand L B The general structural formula is as follows: ligand L C The general structural formula is as follows: m is a metal having an atomic number greater than 40; a. b and c are natural numbers, and the sum of a, b and c is the oxidation number of M; ar (Ar) 1 Is adamantyl and x + y is more than or equal to 1; z is oxygen or sulfur. The ligand of the metal complex provided by the invention contains an adamantane structure, and the metal complex is used as a luminescent layer doping material of a photoelectric device, so that the luminous efficiency and the service life of the photoelectric device can be improved, and the driving voltage of the photoelectric device can be reduced.)
1. A metal complex containing a adamantane structure, wherein the structural formula of the metal complex is as shown in formula I:
M(LA)a(LB)b(LC)c；
I
in the formula, a ligand LAThe general structural formula is as follows:
a. b and c are natural numbers, and the sum of a, b and c is the oxidation number of M;
Ar1is adamantyl and x + y is more than or equal to 1;
z is oxygen or sulfur;
R1、R2、R7and R8The number of substituents each independently comprises is 0 to 4; r3、R4And R5The number of substituents each independently comprises is 0 to 1; r6The number of the substituents is 0 to 2;
R1、R2、R3、R4、R5、R6、R7、R8each independently is at least one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, and substituted or unsubstituted C6-C18 aryl.
2. The metal complex containing a adamantane structure of claim 1, where in the formula, M is one of Ir, Rh, Re, Ru, Os, Pt, Au, and Cu; a is 2, b is 0 or 1, c is 0 or 1, and b and c are not simultaneously 0 or 1.
3. The metal complex containing a adamantane structure of claim 1, where in the substituted or unsubstituted C1-C8 alkyl, at least one C atom is substituted with one of N, O, S, Si, Se, Ge, deuterium, halogen, and cyano; the substituted or unsubstituted C3-C15 cycloalkyl is C3-C10 cycloalkyl; cycloalkyl is monocycloalkyl, polycycloalkyl or spiroalkyl; in the substituted or unsubstituted aryl of C6-C18, the aryl is monocyclic group or polycyclic group; the polycyclic group includes two or more rings having two carbon atoms in two adjoining common, wherein at least one ring is aromatic and the other ring is cycloalkyl, cycloalkenyl, aryl or heteroaryl.
4. The metal complex containing a adamantane structure of claim 3, where the alkyl is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl; the cycloalkyl is selected from cyclopropyl, cyclopentyl, cyclohexyl or adamantyl; the aryl is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl or fluorenyl.
5. The metal complex containing a adamantane structure of claim 3, where in the substituted aryl group of C6-C18, the substituent is deuterium, halogen, cyano, methyl, ethyl, propyl, isopropyl, or phenyl.
6. The metal complex containing a adamantane structure of claim 1, where R is1、R2、R3、R4、R5、R6、R7、R8Each independently selected from at least one of the following groups:
7. the metal complex containing the adamantane structure of claim 1, wherein the chemical formula of the metal complex is any one of formula M001 to formula M099:
8. a process for preparing a metal complex according to any one of claims 1 to 7, comprising the steps of:
ligand LAReacting with halide of M metal to obtain a bridging ligand B;
a bridging ligand B and a ligand LBReacting ethylene glycol ethyl ether with potassium carbonate to obtain the metal complex; or reacting the bridging ligand B with silver trifluoromethanesulfonate to obtain an intermediate C, and reacting the intermediate C with the ligand LCAnd carrying out reaction to obtain the metal complex.
9. An optoelectronic device comprising a first electrode, a second electrode and at least one organic layer disposed between said first electrode and said second electrode, wherein said organic layer comprises a metal complex according to any one of claims 1 to 7.
10. The optoelectronic device according to claim 9, wherein the organic layer comprises a light-emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or entirely contains the metal complex.
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a metal complex containing a adamantane structure, a preparation method thereof and a photoelectric device.
Background
2002-2005 is the growth stage of organic light emitting diodes, and people can widely come into contact with products with organic light emitting diodes, including vehicle-mounted displays, PDAs, mobile phones, DVDs, digital cameras, microdisplays for helmets, and household electrical appliances. Organic light emitting diode products are formally introduced into the market, and mainly enter the display fields of traditional LCD, VFD and the like. In this period, passive driving, single-color or multi-color display, and panels of 10 inches or less have been mainly used, but active driving, full-color, and panels of 10 inches or more have also come into use. In 2005, with the increasing maturity of the organic light emitting diode industrialization technology, the organic light emitting diode began to strike the display market and expand its application field, and the advantages of the organic light emitting diode in each technology were fully explored and exerted. The industrialization of organic light emitting diodes has begun, and it is now the stage where OLED technology is going to mature and market demand is growing at a high rate.
Although there are many new findings on high-efficiency heavy metal phosphors on the market, they have high driving voltage, short lifetime, and low luminous efficiency.
Therefore, it is an urgent technical problem to provide an organic phosphorus light-emitting compound and an organic electroluminescent device having a lower voltage, a longer lifetime and a higher luminous efficiency.
Disclosure of Invention
An object of embodiments of the present invention is to provide a metal complex containing a adamantane structure, so as to solve the problems mentioned in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a metal complex containing a adamantane structure has a general structural formula as shown in formula I:
M(LA)a(LB)b(LC)c；
I
in the formula, a ligand LAThe general structural formula is as follows:
a. b and c are natural numbers, and the sum of a, b and c is the oxidation number of M;
Ar1is adamantyl and x + y is more than or equal to 1;
z is oxygen or sulfur;
R1、R2、R7and R8The number of substituents each independently comprises is 0 to 4; r3、R4And R5The number of substituents each independently comprises is 0 to 1; r6The number of the substituents is 0 to 2;
R1、R2、R3、R4、R5、R6、R7、R8each independently is at least one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, and substituted or unsubstituted C6-C18 aryl.
Preferably, in the formula, M is one of Ir, Rh, Re, Ru, Os, Pt, Au and Cu; a is 2, b is 0 or 1, c is 0 or 1, and b and c are not simultaneously 0 or 1.
Preferably, in the substituted or unsubstituted C1-C8 alkyl, at least one C atom is substituted by one of N, O, S, Si, Se, Ge, deuterium, halogen and cyano; the substituted or unsubstituted C3-C15 cycloalkyl is C3-C10 cycloalkyl; cycloalkyl is monocycloalkyl, polycycloalkyl or spiroalkyl; in the substituted or unsubstituted aryl of C6-C18, the aryl is monocyclic group or polycyclic group; the polycyclic group includes two or more rings having two carbon atoms in two adjoining common, wherein at least one ring is aromatic and the other ring is cycloalkyl, cycloalkenyl, aryl or heteroaryl.
Preferably, the alkyl group is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl; the cycloalkyl is selected from cyclopropyl, cyclopentyl, cyclohexyl or adamantyl; the aryl is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl or fluorenyl.
Preferably, in the substituted aryl group of C6-C18, the substituent is selected from deuterium, halogen, cyano, methyl, ethyl, propyl, isopropyl or phenyl.
Preferably, in the formula, R1、R2、R3、R4、R5、R6、R7、R8Each independently selected from at least one of the following groups:
preferably, the chemical structural formula of the metal complex is any one of formula M001 to formula M099:
another object of an embodiment of the present invention is to provide a method for preparing the metal complex, which includes the following steps:
ligand LAReacting with halide of M metal to obtain a bridging ligand B;
a bridging ligand B and a ligand LBReacting ethylene glycol ethyl ether with potassium carbonate to obtain the metal complex; or reacting the bridging ligand B with silver trifluoromethanesulfonate to obtain an intermediate C, and reacting the intermediate C with the ligand LCAnd carrying out reaction to obtain the metal complex.
Wherein, the ligand LAAnd M a halide of the metal to give a bridged ligand B comprising:
weighing of the ligand LA、IrCl3·3H2O, ethylene glycol ethyl ether and water are respectively added into the reaction systemIn N at2Heating and refluxing for 24h at 120 ℃ under protection, then cooling to room temperature, separating out precipitates, carrying out vacuum filtration, sequentially leaching with water, absolute ethyl alcohol and petroleum ether, and drying to obtain a red powdery bridging ligand B;
the ligand B and the ligand L will be bridgedBThe step of reacting ethylene glycol ethyl ether with potassium carbonate to obtain the metal complex specifically comprises the following steps:
weighing of the bridged ligand B, K2CO3Ethylene glycol ethyl ether is added into the reaction system respectively, and the reaction system is subjected to reaction under the condition of N2Addition of ligand L with protectionBRaising the temperature to 120 ℃, heating and refluxing for 24h, cooling to room temperature, carrying out suction filtration, washing with alcohol, drying, taking dichloromethane as a solvent, carrying out silica gel column chromatography, concentrating the filtrate, and precipitating a solid to obtain the metal complex.
Reacting the bridging ligand B with silver trifluoromethanesulfonate to obtain an intermediate C, and reacting the intermediate C with a ligand LCThe step of reacting to obtain the metal complex specifically comprises:
in the reaction of the bridging ligand B and the silver trifluoromethanesulfonate, the molar ratio of the bridging ligand B to the silver trifluoromethanesulfonate is preferably 1 (2-3); the reaction temperature is preferably 55-65 ℃, and the reaction time is preferably 20-30 h; the reaction is preferably carried out under a protective gas atmosphere; the kind of the protective gas is not particularly limited, and may be a conventional inert gas well known to those skilled in the art, such as nitrogen, argon, etc.; the reaction is carried out in a solvent, preferably one or more of dichloromethane and methanol. In some embodiments, the solvent is a mixed solution of dichloromethane and methanol, wherein the volume ratio of dichloromethane to methanol is 5: 2. The amount of the solvent is not particularly limited, and the reaction raw materials can be sufficiently dissolved. After the reaction, the following post-treatment may preferably be further carried out: cooling, separating by column chromatography, and concentrating. Cooling is preferably to room temperature, and after cooling, column chromatography is carried out, preferably using a short column. After separation, the filtrate is concentrated until solid is separated out, namely an intermediate C.
In intermediate C with ligandsLCIn the reaction of (1), the intermediate C is reacted with a ligand LCThe molar ratio of (A) to (B) is preferably 1 (2-3); the reaction temperature is preferably 75-80 ℃, and the reaction time is preferably 20-30 h. The reaction is preferably carried out under a protective gas atmosphere; the kind of the protective gas is not particularly limited, and may be a conventional inert gas known to those skilled in the art, such as nitrogen, argon, etc. The reaction can be carried out in a solvent, and the solvent is preferably one or more of ethanol and tetrahydrofuran. The amount of the solvent C is not particularly limited, and the reaction raw materials can be sufficiently dissolved. After the reaction, the following post-treatment is preferably also carried out: filtering, washing, drying, column chromatography and concentrating. The washing is preferably an alcohol washing. The drying temperature is preferably 70-80 ℃. In the column chromatography, dichloromethane and petroleum ether are preferably used as solvents according to a certain proportion, and silica gel column chromatography is adopted. And (4) after column chromatography separation, concentrating the filtrate until a solid is separated out, thus obtaining the metal complex.
It is another object of an embodiment of the present invention to provide an optoelectronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, the organic layer comprising the metal complex described above.
Preferably, the organic layer includes a light emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or entirely contains the metal complex.
Specifically, the first electrode is an anode, and the kind thereof is not particularly limited, and may be a conventional anode known to those skilled in the art, and is more preferably one of ITO (indium tin oxide), tin oxide, zinc oxide, and indium oxide. The thickness of the anode is preferably 10-500 nm. The first electrode is a cathode, and the kind thereof is not particularly limited, and may be a conventional cathode known to those skilled in the art, and is more preferably one of Al, Li, Na, K, Mg, Ca, Au, Ag, and Pb. The thickness of the cathode is preferably 100-1000 nm.
The main material is preferably one or more of 4,4'-N, N' -biphenyl dicarbazole (CBP), octahydroxyquinoline (Alq3), metal phenoxybenzothiazole compounds, polyfluorene, aromatic condensed rings and zinc complexes. The mass ratio of the doping material in the light-emitting layer is preferably 0.5% to 10%. The thickness of the light-emitting layer is preferably 10 to 500 nm.
The organic layer may further include other functional layers, and the other functional layers may be specifically selected from one or more of the following functional layers: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a hole injection-hole transport functional layer (i.e., having both hole injection and hole transport functions), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and an electron transport-electron injection functional layer (i.e., having both electron transport and electron injection functions).
The kind of each functional layer is not particularly limited, and may be a conventional functional layer known to those skilled in the art. Preferably: the hole injection layer is one of 2-TNATA (namely N1- (2-naphthyl) -N4, N4-di (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenyl benzene-1, 4-diamine), phthalocyanine and porphyrin compounds, starburst triarylamine, conductive polymer, N-type semiconductive organic complex and metal organic complex; the thickness of the hole injection layer is preferably 10 to 500 nm. The hole transport layer is one of NPB (namely N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine), TPD (namely N, N '-diphenyl-N, N' - (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine), PAPB (namely N, N '-bis (phenanthrene-9-yl) -N, N' -diphenyl benzidine) arylamine carbazole compound and indolocarbazole compound; the thickness of the hole transport layer is preferably 10-500 nm; the thickness of the electron blocking layer is preferably 10-500 nm. The hole blocking layer is one of BAlq, BCP and BPhen; the thickness of the hole blocking layer is preferably 10-500 nm. The electron transport layer is one of Alq3, coumarin No. 6, triazole derivatives, azole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives and anthrone derivatives; the thickness of the electron transport layer is preferably 10-500 nm. The electron injection layer is LiF, CsF or Li2O、Al2O3MgO; the thickness of the electron injection layer is preferably 0.1-10 nm. The thickness of the electron transmission-electron injection functional layer is preferably 10-500 nm. In the present invention, the light-emitting layer and the light-emitting layer can be formed by vapor depositionIts various functional layers.
In addition, the optoelectronic device may include an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), an electronic paper (e-paper), an Organic Photoreceptor (OPC), or an Organic Thin Film Transistor (OTFT), but is not limited thereto.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the metal complex containing the adamantane structure, the ligand of the metal complex contains the adamantane structure, and the metal complex is used as a light-emitting layer doping material of a photoelectric device, so that the light-emitting efficiency and the service life of the photoelectric device can be improved, and the driving voltage of the photoelectric device can be reduced. In addition, the preparation method of the metal complex provided by the embodiment of the invention has simple preparation steps and high product purity.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Compound example 1
The embodiment of the compound provides a metal complex containing a adamantane structure, the chemical structural formula of the metal complex is a formula M001 in the invention, and the reaction route of the preparation method of the metal complex is as follows:
the specific preparation method comprises the following steps:
s1, weighing A001(65.91mmo1, 20g) and IrCl under the protection of nitrogen33H2O (21.97mmo1, 7.55g) is put into a reaction system, a mixed solution of 400mL of ethylene glycol ethyl ether and 133mL of purified water is added, reflux reaction is carried out at 120 ℃ for 24 hours under the protection of nitrogen, the system is cooled to room temperature after the reaction is stopped, precipitates are separated out, the precipitates are filtered, water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence, and the orange-red powdery bridging ligand B001(14.6g, the yield is high80.5%); its Mw theoretical value: 1651.0, test value: 1650.6.
s2, weighing orange red powdery bridging ligand B001(8.48mmol, 14g), adding 2.55g ligand pentane-2, 4-diketone C001, adding 400mL ethylene glycol ethyl ether and 11.72g potassium carbonate into the system, stirring for 24 hours at 120 ℃ under the protection of nitrogen, performing suction filtration, alcohol washing, drying, using dichloromethane as a solvent, performing silica gel column chromatography, and concentrating and separating out solid from filtrate to obtain a final red compound M001(10.2g, yield 67.1%); its HPLC purity was: greater than 99%; mass spectrum: calculated value 896.1, test value 896.3; elemental analysis was as follows:
calculated value C: 65.67 percent; h: 6.19 percent; n: 3.13 percent; o: 3.57 percent; ir: 21.45 percent;
test value C: 65.69 percent; h: 6.21 percent; n: 3.12 percent; o: 3.56 percent; ir: 21.45 percent.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, thereby proving that the complex can be successfully synthesized by the technical scheme disclosed by the invention.
Compound example 2
The embodiment of the compound provides a metal complex containing a adamantane structure, the chemical structural formula of the metal complex is M017 in the summary of the invention, and the reaction route of the preparation method of the metal complex is as follows:
the specific preparation method comprises the following steps:
s1, weighing the compound A017(31.8mmol, 10.0g) and IrC1 under the protection of nitrogen3·3H2O (12.23mmol, 4.31g) was added to the reaction system, and a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water was added thereto, followed by reflux at 130 ℃ for 24 hours under nitrogen protection. Then, the mixture was cooled to room temperature, and a precipitate was precipitated, which was filtered, washed with water, absolute ethanol, and petroleum ether in this order, and then dried, to obtain bridging ligand B017(6.8g, yield 65%) in the form of yellow powder.
S2, weighing bridging ligand B017(3.80mmol, 6.5g), adding silver trifluoromethanesulfonate (11.41mmol, 2.93g), adding 100mL of dichloromethane and 40mL of methanol into the system, and refluxing at 55 ℃ for 24 hours under the protection of nitrogen. After that, the mixture was cooled to room temperature, and the column chromatography (short column) filtrate was concentrated to precipitate a solid, thereby obtaining intermediate C017(7.1g, yield 90.6%) as a yellow-green powder.
Wherein, the column chromatography conditions are as follows: selecting dichloromethane and petroleum ether as a solvent, weighing 470g of silica gel (200-300 meshes) as an adsorbent, adding petroleum ether, fully stirring until the mixture is uniform, pouring the mixture into a column, and adding a mixture after the silica gel is settled, wherein the developing agent is dichloromethane: petroleum ether is 1: 1, purifying it using the eluent.
S3, weighing intermediate C017(6.79mmol, 9g), adding ligand D017(20.38mmol, 5.33g), adding 120mL of absolute ethanol into the system, and refluxing at 75 ℃ for 24 hours under the protection of nitrogen. Then, the reaction mixture was subjected to suction filtration, alcohol washing and drying, and then subjected to silica gel column chromatography using dichloromethane as a solvent, and the filtrate was concentrated until a solid precipitated, to obtain yellow compound M017(4.2g, yield 57.2%).
Wherein, the conditions of the silica gel column chromatography are as follows: the solvent is dichloromethane and petroleum ether, the adsorbent is silica gel (200-300 meshes), 440g is weighed, the petroleum ether is added, the mixture is poured into a column after the silica gel is settled, and the mixture is added, wherein the developing agent is dichloromethane: petroleum ether is 1: and 8, purifying the eluent.
The detection analysis of the obtained compound M017 showed the following results:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 1079.35; the test value was 1079.38.
Elemental analysis:
the calculated values are: c: 67.88 percent; h: 4.86 percent; n: 6.49 percent; s: 2.97 percent; ir: 17.81 percent;
the test values are: c: 67.89 percent; h: 4.87 percent; n: 6.48 percent; s: 2.98 percent; ir: 17.80 percent.
From the above test results, it can be seen that the compound of M017 structure can be prepared with high purity according to the embodiment of the present invention.
Compound example 3
The embodiment of the compound provides a metal complex containing a adamantane structure, the chemical structural formula of the metal complex is shown as formula M030 in the summary of the invention, and the reaction route of the preparation method of the metal complex is as follows:
the specific preparation method comprises the following steps:
s1, weighing A030(69.11mmo1, 20g) and IrCl under the protection of nitrogen33H2O (23.04mmo1, 8.12g) is put into a reaction system, a mixed solution of 400mL of ethylene glycol ethyl ether and 133mL of purified water is added, reflux reaction is carried out at 120 ℃ for 24 hours under the protection of nitrogen, the system is cooled to room temperature after the reaction is stopped, precipitates are separated out, the precipitates are filtered, and water, absolute ethyl alcohol and petroleum ether are sequentially washed and dried to obtain orange red powdery bridging ligand B030(12.8g, the yield is 69%); its Mw theoretical value: 1608.96, test value: 1608.56.
s2, weighing orange red powdery bridging ligand B030(7.46mmol, 12g), adding 4.75g of ligand 3, 7-diethylnonane-4, 6-dione C030, adding 400mL of ethylene glycol ethyl ether and 10.31g of potassium carbonate into the system, stirring at 120 ℃ for 24 hours under the protection of nitrogen, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as a solvent, carrying out silica gel column chromatography, concentrating the filtrate, and precipitating a solid to obtain a final red compound M030(9.6g, yield 65.65%); its HPLC purity was: greater than 99%; mass spectrum: calculated value 980.34, test value 980.48; elemental analysis was as follows:
calculated value C: 67.38 percent; h: 6.89 percent; n: 2.86 percent; o: 3.26 percent; ir: 19.61 percent;
test value C: 67.37 percent; h: 6.88 percent; n: 2.87 percent; o: 3.25 percent; ir: 19.60 percent.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, thereby proving that the complex can be successfully synthesized by the technical scheme disclosed by the invention.
Compound example 4
The embodiment of the compound provides a metal complex containing a adamantane structure, the chemical structural formula of the metal complex is shown as the formula M045 in the summary of the invention, and the reaction route of the preparation method of the metal complex is as follows:
the specific preparation method comprises the following steps:
s1, weighing A045(69.11mmo1, 20g) and IrCl under the protection of nitrogen33H2O (23.04mmo1, 8.12g) is put into a reaction system, a mixed solution of 400mL of ethylene glycol ethyl ether and 133mL of purified water is added, reflux reaction is carried out at 120 ℃ for 24 hours under the protection of nitrogen, the system is cooled to room temperature after the reaction is stopped, a precipitate is separated out, the precipitate is filtered, and water, absolute ethyl alcohol and petroleum ether are sequentially washed and dried to obtain a bridge-linked ligand B045(12.3g, the yield is 66.37%) in an orange-red powder shape; its Mw theoretical value: 1608.96, test value: 1608.56.
s2, weighing orange red powdery bridging ligand B045(7.46mmol, 12g), adding 4.66g ligand hexafluoropentane-2, 4-dione C045, adding 400mL ethylene glycol ethyl ether and 10.31g potassium carbonate into the system, stirring at 120 ℃ for 24 hours under the protection of nitrogen, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as a solvent, carrying out silica gel column chromatography, concentrating the filtrate to precipitate solid, and obtaining a final red compound M045(11.1g, yield 76.24%); its HPLC purity was: greater than 99%; mass spectrum: calculated value 976.07, test value 976.3; elemental analysis was as follows:
calculated value C: 57.83 percent; h: 4.65 percent; n: 2.87 percent; o: 3.28 percent; ir: 19.69 percent; f: 11.68 percent;
test value C: 57.84 percent; h: 4.64 percent; n: 2.87 percent; o: 3.26 percent; ir: 19.68 percent; f: 11.67 percent.
The comparison of the calculated value and the test value proves that the measured value is basically consistent with the theoretical value, thereby proving that the complex can be successfully synthesized by the technical scheme disclosed by the invention.
Compound example 5
The embodiment of the compound provides a metal complex containing a adamantane structure, the chemical structural formula of the metal complex is shown as the formula M047 in the invention, and the reaction route of the preparation method of the metal complex is as follows:
the specific preparation method comprises the following steps:
s1, weighing Compound A047(27.81mmol, 10.0g) and IrC1 under nitrogen protection system3·3H2O (10.7mmol, 3.77g) was added to the reaction system, and a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water was added thereto, followed by reflux at 130 ℃ for 24 hours under nitrogen protection. Then, the reaction mixture was cooled to room temperature, and a precipitate was precipitated, which was filtered under suction, washed with water, absolute ethanol, and petroleum ether in this order, and then dried, to obtain bridging ligand B047(6.7g, yield 67.92%) as a yellow powder.
S2, the bridging ligand B047(3.52mmol, 6.5g) was weighed, silver trifluoromethanesulfonate (10.57mmol, 2.72g) was added, and 100mL of dichloromethane and 40mL of methanol were added to the system, and the mixture was refluxed at 55 ℃ for 24 hours under nitrogen protection. After that, it was cooled to room temperature, and the column chromatography (short column) filtrate was concentrated to precipitate a solid, to obtain intermediate C047(6.8g, yield 86.1%) as a yellow-green powder.
Wherein, the column chromatography conditions are as follows: selecting dichloromethane and petroleum ether as a solvent, weighing 473g of silica gel (200-300 meshes) as an adsorbent, adding petroleum ether, fully stirring until the mixture is uniform, pouring the mixture into a column, and adding a mixture after the silica gel is settled, wherein the developing agent is dichloromethane: petroleum ether is 1: 1, purifying it using the eluent.
S3, weighing intermediate C047(5.80mmol, 6.5g), adding ligand D047(17.4mmol, 4.55g), adding 120mL of absolute ethanol into the system, and refluxing at 75 ℃ for 24 hours under the protection of nitrogen. Then, the reaction mixture was subjected to suction filtration, alcohol washing and drying, and then silica gel column chromatography using dichloromethane as a solvent was performed, and the filtrate was concentrated until a solid precipitated, to obtain a yellow compound M047(5.1g, yield 75.16%).
Wherein, the conditions of the silica gel column chromatography are as follows: selecting dichloromethane and petroleum ether as a solvent, weighing 407g of an adsorbent which is silica gel (200-300 meshes), adding petroleum ether, fully stirring until the mixture is uniform, pouring the mixture into a column, and adding a mixture after the silica gel is settled, wherein the developing agent is dichloromethane: petroleum ether is 1: and 8, purifying the eluent.
The compound M047 obtained was subjected to detection analysis, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 1169.62; the test value was 1169.52.
Elemental analysis:
the calculated values are: c: 70.85 percent; h: 6.38 percent; n: 3.59 percent; s: 2.74 percent; ir: 16.43 percent;
the test values are: c: 70.86 percent; h: 6.37 percent; n: 3.60 percent; s: 2.75 percent; ir: 16.44 percent.
As can be seen from the above test results, example 5 prepared a compound of M047 structure with high purity.
The synthetic routes and principles of the preparation methods of other metal complexes with the structural general formula of formula I in the summary of the invention are the same as those of the compound example 1 or the compound example 2 listed above, so that the process is not exhaustive, and a plurality of metal complexes are selected as the compound examples 6-20 in the invention, which are specifically as follows.
Examples 6 to 20 of the Compounds
The preparation method of the compound example 1 or the compound example 2 is followed, and the raw materials are respectively replaced by the compounds corresponding to the corresponding ligand structures in the target product, so that a series of metal complexes are obtained, as shown in the following table 1.
TABLE 1
Examples of the Compounds
Structural formula (I)
Molecular formula
Theoretical value of mass spectrum
Mass spectrometric test values
Purity of
Compound example 6
M003
C51H59IrN2O2
924.24
924.42
＞99％
Compound example 7
M005
C65H62IrN3S
1109.48
1109.42
＞99％
Compound example 8
M006
C55H67IrN2O2
980.34
980.48
＞99％
Compound example 9
M007
C67H70IrN3S
1141.57
1141.49
＞99％
Compound example 10
M010
C49H49D6IrN2O2
902.22
902.42
＞99％
Compound example 11
M050
C69H68IrN3S
1163.58
1163.47
＞99％
Compound example 12
M054
C59H49D10IrN2O2
1030.39
1030.48
＞99％
Compound example 13
M058
C47H45F6IrN2O2
976.07
976.30
＞99％
Compound example 14
M065
C64H64IrN3S
1099.49
1099.44
＞99％
Compound example 15
M068
C63H50D12IrN3S
1097.54
1097.50
＞99％
Compound example 16
M071
C72H51D10IrN4S
1216.62
1216.48
＞99％
Compound example 17
M081
C53H50D5IrN2O2
949.26
949.42
＞99％
Compound example 18
M089
C65H53D5IrN3S
1110.48
1110.42
＞99％
Compound example 19
M091
C52H61IrN2O2
938.26
938.43
＞99％
Compound example 20
M099
C57H53D18IrN2O2
1026.51
1026.62
＞99％
The embodiment of the present invention further provides a photoelectric device prepared by using the metal complex provided in the above embodiment, and specifically, the photoelectric device is an organic electroluminescent device, where the organic electroluminescent device includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode.
The organic layer may include at least one of a hole injection layer, a hole transport layer, a composite layer of hole injection and hole transport technical layers, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron transport layer, and a composite layer of electron injection technical layers, and at least one of the layers may or may not include the metal complex.
Specifically, the light-emitting layer includes a host material and a dopant material; wherein, the main material can be 4,4'-N, N' -biphenyl dicarbazole, but is not limited to the above; the doping material may be selected from the above-mentioned metal complexes.
In practical applications, the method for manufacturing the organic electroluminescent device can refer to device example 1 and device example 9 described below.
Device example 1
Embodiment 1 of the device provides a green phosphorescence doped organic electroluminescent device, which has the structure of ITO anode/HIL/HTL/EML/HBL/ETL/EIL/cathode, and the preparation method of the organic electroluminescent device comprises the following steps:
a. an ITO anode: coating with a thickness of
b. HIL (hole injection layer): a hole injection layer was formed by evaporation of 2-TNATA (N1- (2-naphthyl) -N4, N4-bis (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenylbenzene-1, 4-diamine) at 60 nm.
c. HTL (hole transport layer): NPB (i.e., N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine) was evaporated to 60nm to form a hole transport layer.
d. EML (light-emitting layer): a host material CBP (namely 4,4'-N, N' -biphenyl dicarbazole) and a doping material-metal complex M005 are mixed and evaporated for 30nm according to the weight ratio of 90: 10 to form a light-emitting layer.
e. HBL (hole blocking layer): a hole blocking layer was formed by evaporation of BALq 10 nm.
f. ETL (electron transport layer): steaming foodAlq plating340nm, forming an electron transport layer.
g. EIL (electron injection layer): and evaporating LiF by 0.2nm to form an electron injection layer.
h. Cathode: and evaporating Al with the thickness of 150nm to form an anode, thereby obtaining the organic electroluminescent device.
Device examples 2 to 8
Device embodiments 2 to 8 are prepared by referring to the preparation method provided in the device embodiment 1, except that the metal complex M005 in the device embodiment 1 is replaced with metal complexes M007, M017, M050, M065, M068, M071 and M089, respectively.
Device example 9
Embodiment 9 of the device provides a red-light phosphorescence doped organic electroluminescent device, which has an ITO anode/HIL/HTL/EML/HBL/ETL/EIL/cathode structure, and the preparation method of the organic electroluminescent device comprises the following steps:
a. an ITO anode: coating with a thickness ofThe ITO (indium tin oxide) glass substrate is cleaned in distilled water for 2 times, ultrasonically cleaned for 30min, then repeatedly cleaned for 2 times by distilled water, ultrasonically cleaned for 10min, after the cleaning is finished, ultrasonically cleaned by methanol, acetone and isopropanol in sequence (each time for 5min), dried, then transferred into a plasma cleaning machine for cleaning for 5min, and then sent into an evaporation machine, and other functional layers are sequentially evaporated on the substrate by taking the substrate as an anode.
b. HIL (hole injection layer): a hole injection layer was formed by evaporation of 2-TNATA (N1- (2-naphthyl) -N4, N4-bis (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenylbenzene-1, 4-diamine) at 60 nm.
c. HTL (hole transport layer): NPB (i.e., N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine) was evaporated to 60nm to form a hole transport layer.
d. EML (light-emitting layer): a host material CBP (namely 4,4'-N, N' -biphenyl dicarbazole) and a doping material-metal complex M001 are mixed and evaporated for 30nm according to the weight ratio of 90: 10 to form a light-emitting layer.
e. HBL (hole blocking layer): a hole blocking layer was formed by evaporation of BALq 10 nm.
f. ETL (electron transport layer): evaporation Alq340nm, forming an electron transport layer.
g. EIL (electron injection layer): and evaporating LiF by 0.2nm to form an electron injection layer.
h. Cathode: and evaporating Al with the thickness of 150nm to form an anode, thereby obtaining the organic electroluminescent device.
Device examples 10 to 20
Device examples 10 to 20 were prepared with reference to the preparation method provided in device example 9 above, except that the metal complex M001 in device example 9 above was replaced with metal complexes M003, M006, M010, M030, M045, M047, M054, M058, M081, M091, and M099, respectively.
Comparative device example 1
An organic electroluminescent device was fabricated in the same manner as in device example 1, except that the dopant material in the light-emitting layer was replaced with the compound Ir (ppy)3The structure is as follows:
comparative device example 2
An organic electroluminescent device was fabricated as in device example 9, except that the dopant material in the light-emitting layer was replaced with the compound Ir (pq)2acac, the structure of which is as follows:
experimental example:
1. the organic electroluminescent devices obtained in the device examples 1 to 8 and the device comparative example 1 were respectively tested for luminescence performance, specifically, the driving voltage, the luminescence lifetime (T95) and the luminescence efficiency of the organic electroluminescent device were tested under a certain luminance condition, and the test results are shown in table 2 below.
TABLE 2
2. The organic electroluminescent devices obtained in the device examples 9 to 20 and the device comparative example 2 were respectively subjected to luminescence property detection, specifically, the driving voltage, the luminescence lifetime (T95) and the luminescence efficiency of the organic electroluminescent device were measured under a certain luminance condition, and the test results are shown in table 3 below.
TABLE 3
As can be seen from the above tables 2 to 3, compared with the existing organic electroluminescent devices provided by the comparative device examples 1 to 2, the organic electroluminescent device prepared by using the metal complex provided by the embodiment of the invention can effectively reduce the driving voltage of the organic electroluminescent device, and greatly improve the luminous efficiency and the service life of the organic electroluminescent device.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.