Fused ring compound and preparation method and application thereof
阅读说明：本技术 一种稠环化合物及其制备方法和应用 (Fused ring compound and preparation method and application thereof ) 是由 李祥智 蔡烨 魏定纬 陈志宽 于 2019-09-04 设计创作，主要内容包括：本发明公开了一种稠环化合物及其制备方法和应用。所述的稠环化合物,具有如式(I)或式(II)所示的结构。所述的稠环化合物,其HOMO和LUMO能级完全分离,在降低材料的能隙宽度的同时,提高三线态能级,避免客体材料到主体材料的能量倒流而降低发光效率；HOMO和LUMO能级与相邻材料匹配,驱动电压较小；其分子结构尺寸较大,分子内共轭性较好,因此具有较好的热稳定性,能够避免在成膜或使用过程材料受热分解,避免材料层功能的丧失,提高器件的发光效率和发光性能。本发明还提供了上述稠环化合物的制备方法及其作为有机电致发光材料的应用。(The invention discloses a fused ring compound and a preparation method and application thereof. The fused ring compound has a structure shown as a formula (I) or a formula (II). The HOMO energy level and the LUMO energy level of the condensed ring compound are completely separated, so that the triplet state energy level is improved while the energy gap width of the material is reduced, and the light-emitting efficiency is prevented from being reduced due to energy backflow from an object material to a host material; HOMO and LUMO energy levels are matched with adjacent materials, and the driving voltage is small; the molecular structure of the material is large in size, and the intramolecular conjugation property is good, so that the material has good thermal stability, the material can be prevented from being heated and decomposed in the process of film formation or use, the loss of the function of a material layer is avoided, and the luminous efficiency and the luminous performance of a device are improved. The invention also provides a preparation method of the fused ring compound and application of the fused ring compound as an organic electroluminescent material.)
1. A fused ring compound having a structure represented by formula (I) or formula (II):
R1-R14independently of one another, from hydrogen, deuterium, halogen, cyano, hydroxyl, nitro, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C2-C60Alkenyl of (a), substituted or unsubstituted C2-C60Alkynyl, substituted or unsubstituted C1-C60Alkylamino group of (A), substituted or unsubstituted C2-C60Substituted or unsubstituted C2-C60Alkynylamino, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C2-C60Alkenyloxy of (a), substituted or unsubstituted C2-C60Alkynyloxy of, substituted or unsubstituted C1-C60Thioalkoxy, substituted or unsubstituted C2-C60Thioalkenyloxy, substituted or unsubstituted C2-C60With a thioalkynyloxy group, substituted or unsubstituted C1-C60With an alkyl boron group, substituted or unsubstituted C2-C60With an alkene boron group, substituted or unsubstituted C2-C60With a boron alkynyl group, substituted or unsubstituted C1-C60Ester group of (1), substituted or unsubstituted C1-C60Amide group of (A), substituted or unsubstituted C4-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C4-C60Aryloxy group of (1), substituted or unsubstituted C4-C60With an aromatic amine group, substituted or unsubstituted C4-C60Of a thioaromatic compoundOxy, substituted or unsubstituted C4-C60An arylboron group of, or
R1-R14Any two to four adjacent groups of which are linked to form one or more groups of rings A,
the ring A is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C60Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring;
Ar1selected from a group P substituted or unsubstituted with one or more substituents selected from:
C4-C60aryl of (C)3-C60Heteroaryl of (A), C4-C60Aryloxy group of (A), C4-C60Aromatic amine group of (2), C4-C60Thioaryloxy of (C)4-C60Aryl boron group of (A), C4-C60Aryl phosphine group of (A), C4-C60Heteroaryloxy of (A), C4-C60Heteroaromatic amino group of (1), C4-C60Thio-heteroaryloxy of (A), C4-C60Heteroaryl boron group of (A), C4-C60The heteroaromatic phosphine group of (1);
the substituents are independently of one another selected from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkenyl of (a), halogen-substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)3-C12Heteroaryl of (A), C3-C12A heteroaryl amine of (a), halogen-substituted C3-C12Heteroaryl, deuterium substituted C of3-C12The heteroaryl group of (a).
2. The fused ring compound of claim 1,
Ar1is composed of
R15independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30Arylboron group of (A), substituted or unsubstituted C4-C30An aryl phosphorus group of, or
Two adjacent R15Are connected to form a ring B,
the ring B is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring; or
Ar1Is selected from
T1-T2independently of one another, selected from the group consisting of the connecting bonds O, S, SO2、CO、NR17、C(R17)2、POR17，
n1 is an integer of 0 to 3, n2 is an integer of 0 to 4, n3 is an integer of 0 to 3, n4 is an integer of 0 to 4,
R16independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30Arylboron group of (A), substituted or unsubstituted C4-C30An aryl phosphorus group of, or
Two adjacent R16Are connected to form a ring C,
the ring C is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, the heterocycle is a saturated or unsaturated ring,
R17independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30An arylboron group of, or
Two adjacent R17Are connected to form a ring D,
the ring D is selected from a substituted or unsubstituted cyclic 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring; or
Ar1Is composed ofY is NR18Or CR18Or O or S, NR18The number of (a) is 0 to 3,it is shown that the connecting key is,
R18independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30An arylboron group of, or
Two adjacent R18Are connected to form a ring E,
the ring E is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocyclic ring isA saturated or unsaturated ring, and the heterocyclic ring is a saturated or unsaturated ring.
3. The fused ring compound of claim 1 or 2,
Ar1selected from the group consisting of19A substituted or unsubstituted group F selected from:
the substituent R19Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkenyl of (a), halogen-substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)2-C12Heteroaryl of (A), C2-C12A heteroaryl amine of (a), halogen-substituted C2-C12Heteroaryl, deuterium substituted C of2-C12The heteroaryl group of (a);
preferably, the substituent R19Are connected with each otherIndependently selected from hydrogen, deuterium, halogen, methyl, deuterated methyl, trifluoromethyl, ethyl, propyl, tert-butyl, cyano, vinyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl or grate, benzofuranyl, benzothienyl, carbazolyl,
wherein the content of the first and second substances,indicating a bond, ＊ indicating a binding site.
4. The fused ring compound of any one of claims 1-3, wherein Ar is Ar1Are electron withdrawing groups.
5. A fused ring compound according to any one of claims 1 to 4,
R1-R14independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkenyl of (a), halogen-substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)2-C12Heteroaryl of (A), C2-C12A heteroaryl amine of (a), halogen-substituted C2-C12Heteroaryl, deuterium substituted C of2-C12The heteroaryl group of (a); or
R1-R14Any two to four adjacent groups of which are linked to form one or more groups of rings A,
the ring A is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C12Aryl of (2)Or substituted or unsubstituted C3-C12The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring;
preferably, R1-R14Independently of one another, from the group consisting of hydrogen, deuterium, halogen, methyl, ethyl, propyl, n-butyl, tert-butyl, trifluoromethyl, cyano, phenyl, biphenyl, terphenyl, pentalenyl, indenyl, naphthyl, azulenyl, heptalenyl, adamantyl, bornyl, triphenylene, indacenyl, acenaphthenyl, fluorenyl, spirobifluorenyl, benzofluorenyl, dibenzofluorenyl, phenalenyl, phenanthrenyl, anthracenyl, fluoranthryl, benzophenanthrenyl, pyrenyl, chrysenyl, tetracenyl, picenyl, perylenyl, pentylphenyl, pentacenyl, rubinyl, coronenyl, ovaphenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, thienyl, furyl, quinolyl, carbazolyl, pyranyl, thiopyranyl, phthalazinyl, phenazinyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, indolyl, indolocarbazolyl, phenanthridinyl, acridinyl, terphenyl, phenanthridinyl, phenanthrenyl, perimidine group, pteridinyl group, quinazolinyl group, quinoxalinyl group, cinnolinyl group, phenanthroline group, carbolinyl group, benzofuranyl group, benzothienyl group, dibenzofuranyl group, dibenzothiophenyl group, benzonaphthofuranyl group, dinaphthofuranyl group, benzocarbazolyl group, dibenzocarbazolyl group, dibenzothiapyrrolyl group, benzonaphthothiapyrrolyl group, dinaphthothiazolyl group, benzimidazolyl group, imidazopyridinyl group.
6. A fused ring compound according to any one of claims 1 to 5, having a molecular structure represented by any one of:
7. a process for the preparation of a fused ring compound as claimed in any one of claims 1 to 6,
the synthesis steps of the compound shown in the formula (I) are as follows:
taking a compound shown in a formula (A) and a compound shown in a formula (B) as initial raw materials, and carrying out Suzuki coupling reaction to obtain an intermediate 1-A; carrying out coupling reaction on the intermediate 1-A and a compound shown as a formula (C) to obtain an intermediate 2-A; carrying out coupling reaction on the intermediate 2-A and a compound shown as a formula (D) to obtain an intermediate 3-A; carrying out coupling and ring-closing reaction on the intermediate 3-A to obtain an intermediate 4-A; carrying out nitro reduction and ring closure reaction on the intermediate 4-A to obtain an intermediate 5-A; carrying out coupling reaction on the intermediate 5-A and a compound shown as a formula (E) to obtain a compound shown as a formula (I);
the synthetic route of the compound shown in the formula (I) is shown as follows:
the synthesis steps of the compound shown in the formula (II) are as follows:
taking a compound shown in a formula (F) and a compound shown in a formula (G) as initial raw materials, and carrying out Suzuki coupling reaction to obtain an intermediate 1-B; carrying out coupling reaction on the intermediate 1-B and a compound shown as a formula (H) to obtain an intermediate 2-B; carrying out coupling reaction on the intermediate 2-B and a compound shown as a formula (J) to obtain an intermediate 3-B; the intermediate 3-B is subjected to coupling ring-closing reaction to obtain an intermediate 4-B; carrying out nitro reduction and ring closure reaction on the intermediate 4-B to obtain an intermediate 5-B; carrying out coupling reaction on the intermediate 5-B and a compound shown as a formula (K) to obtain a compound shown as a formula (II);
the synthetic route of the compound shown in the formula (II) is shown as follows:
8. an electronic device comprising a substrate, a first electrode formed on the substrate, a second electrode, an organic layer provided between the first electrode and the second electrode, the organic layer comprising the fused ring compound according to any one of claims 1 to 6;
the organic layer comprises at least one of a luminescent layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole blocking layer and an electron blocking layer;
the light-emitting layer includes a host material containing the condensed ring compound according to any one of claims 1 to 6 and a dopant material.
9. A display device characterized by comprising the electronic device according to claim 8.
10. A lighting device comprising the electronic device of claim 8.
Technical Field
The invention relates to the technical field of display, in particular to a fused ring compound and a preparation method and application thereof.
Background
In 1987, dane cloud doctor in the laboratory of Kodak corporation of america (Eastman Kodak) first made the first organic light-emitting diode (OLED) device by vacuum evaporation, and used transparent and conductive Indium Tin Oxide (ITO) as the anode, and evaporated diamine derivative and tris (8-hydroxyquinoline) aluminum on the anode in sequence, and used magnesium-silver alloy as the cathode material, and this multilayer structure can reduce the driving voltage of the OLED device, and effectively improve the charge injection problem between the material molecules and the electrode interface, and the device performance and lifetime are also improved accordingly.
Compared with an inorganic electroluminescent device (ELD), the OLED device has many advantages of low driving voltage, high luminous efficiency, high contrast, high color saturation, wide viewing angle, fast response time, and the like. In the prior art, an OLED device generally includes a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and is matched with appropriate electrodes, and each of the layers is respectively composed of the following materials: hole injection materials, hole transport materials, light emitting materials, hole blocking materials, electron transport materials, electron injection materials. The OLED light-emitting layer manufactured by adopting a doping mode has advantages in the light-emitting efficiency of the device, so that the light-emitting layer material is usually formed by doping a host material with a guest material, and the host material is an important factor influencing the light-emitting efficiency and the performance of the OLED device. 4,4' -Bis (9H-carbazol-9-yl) biphenol (CBP) is a widely used host material for a light-emitting layer, and has good hole transport properties, but when CBP is used as a host material, the CBP has a low glass transition temperature and is easily recrystallized, so that the service performance and the light-emitting efficiency of an OLED device are reduced, and in addition, CBP is a hole-type host material, the transport of electrons and holes is not balanced, the recombination efficiency of excitons is low, and a light-emitting region is not ideal, and the roll-off phenomenon of the OLED device is severe during operation, so that the efficiency of energy transfer from the host material to a guest material is low, and further, the device efficiency is reduced.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to overcome the defects of low stability of the host material of the light emitting layer, low energy transfer efficiency, low light emitting efficiency of the device, and short service life in the prior art, so as to provide a condensed ring compound, and a preparation method and an application thereof.
In a first aspect, the present invention provides a fused ring compound having a structure represented by formula (I) or formula (II):
R1-R14independently of one another, from hydrogen, deuterium, halogen, cyano, hydroxyl, nitro, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C2-C60Alkenyl of (a), substituted or unsubstituted C2-C60Alkynyl, substituted or unsubstituted C1-C60Alkylamino group of (A), substituted or unsubstituted C2-C60Substituted or unsubstituted C2-C60Alkynylamino, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C2-C60Of (a) is an alkylene oxideRadical, substituted or unsubstituted C2-C60Alkynyloxy of, substituted or unsubstituted C1-C60Thioalkoxy, substituted or unsubstituted C2-C60Thioalkenyloxy, substituted or unsubstituted C2-C60With a thioalkynyloxy group, substituted or unsubstituted C1-C60With an alkyl boron group, substituted or unsubstituted C2-C60With an alkene boron group, substituted or unsubstituted C2-C60With a boron alkynyl group, substituted or unsubstituted C1-C60Ester group of (1), substituted or unsubstituted C1-C60Amide group of (A), substituted or unsubstituted C4-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C4-C60Aryloxy group of (1), substituted or unsubstituted C4-C60With an aromatic amine group, substituted or unsubstituted C4-C60Thioaryloxy, substituted or unsubstituted C4-C60An arylboron group of, or
R1-R14Any two to four adjacent groups of which are linked to form one or more groups of rings A,
the ring A is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C60Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring;
Ar1selected from a group P substituted or unsubstituted with one or more substituents selected from:
C4-C60aryl of (C)3-C60Heteroaryl of (A), C4-C60Aryloxy group of (A), C4-C60Aromatic amine group of (2), C4-C60Thioaryloxy of (C)4-C60Aryl boron group of (A), C4-C60Aryl phosphine group of (A), C4-C60Heteroaryloxy of (A), C4-C60Heteroaromatic amino group of (1), C4-C60Thio-heteroaryloxy of (A), C4-C60Heteroaryl boron group of (A), C4-C60The heteroaromatic phosphine group of (1);
the substituents are independently of one another selected from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkenyl of (a), halogen-substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)2-C12Heteroaryl of (A), C2-C12A heteroaryl amine of (a), halogen-substituted C2-C12Heteroaryl, deuterium substituted C of2-C12The heteroaryl group of (a).
Further, in the above-mentioned fused ring compound,
Ar1is composed of
R15independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30Substituted or unsubstituted arylamine groups ofC4-C30Thioaryloxy, substituted or unsubstituted C4-C30Arylboron group of (A), substituted or unsubstituted C4-C30An aryl phosphorus group of, or
Two adjacent R15Are connected to form a ring B,
the ring B is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring; or
Ar1Is selected from
R16independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30Arylboron group of (A), substituted or unsubstituted C4-C30An aryl phosphorus group of, or
Two adjacent R16Are connected to form a ring C,
the ring C is selected from substituted orUnsubstituted 3-7 membered carbocyclic ring, substituted or unsubstituted 3-7 membered heterocyclic ring, substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, the heterocycle is a saturated or unsaturated ring,
R17independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30An arylboron group of, or
Two adjacent R17Are connected to form a ring D,
the ring D is selected from a substituted or unsubstituted cyclic 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring; or
Ar1Is composed of
R18independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, amino, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl, substituted or notSubstituted C4-C30Aryl, substituted or unsubstituted C3-C30Heteroaryl, substituted or unsubstituted C4-C30Aryloxy group of (1), substituted or unsubstituted C4-C30With an aromatic amine group, substituted or unsubstituted C4-C30Thioaryloxy, substituted or unsubstituted C4-C30An arylboron group of, or
Two adjacent R18Are connected to form a ring E,
the ring E is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C30Aryl or substituted or unsubstituted C3-C30The carbocyclic ring is a saturated or unsaturated ring, and the heterocyclic ring is a saturated or unsaturated ring.
Further, in the above-mentioned fused ring compound,
Ar1selected from the group consisting of19A substituted or unsubstituted group F selected from:
the substituent R19Independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4An alkenyl group of,Halogen substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)2-C12Heteroaryl of (A), C2-C12A heteroaryl amine of (a), halogen-substituted C2-C12Heteroaryl, deuterium substituted C of2-C12The heteroaryl group of (a);
preferably, the substituent R19Independently of one another, from hydrogen, deuterium, halogen, methyl, deuterated methyl, trifluoromethyl, ethyl, propyl, tert-butyl, cyano, vinyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl or grate, benzofuranyl, benzothienyl, carbazolyl,
wherein the content of the first and second substances,
Further, in the above-mentioned condensed ring compound, Ar is1Are electron withdrawing groups.
Further, in the above-mentioned fused ring compound,
R1-R14independently of one another, from hydrogen, deuterium, halogen, nitro, cyano, C1-C4Alkyl, halogen substituted C1-C4Alkyl, deuterium substituted C1-C4Alkyl of (C)1-C4Alkoxy group of (C)1-C4Alkenyl of (a), halogen-substituted C1-C4Alkenyl, deuterium substituted C1-C4Alkenyl of, C6-C12Aryl of (C)6-C12Aryloxy group of (A), C6-C12Arylamino, halogen-substituted C6-C12Aryl, deuterium substituted C of6-C12Aryl of (C)2-C12Heteroaryl of (A), C2-C12A heteroaryl amine of (a), halogen-substituted C2-C12Heteroaryl, deuterium substituted C of2-C12The heteroaryl group of (a); or
R1-R14Any two to four adjacent groups of which are linked to form one or more groups of rings A,
the ring A is selected from a substituted or unsubstituted 3-7 membered carbocyclic ring, a substituted or unsubstituted 3-7 membered heterocyclic ring, a substituted or unsubstituted C4-C12Aryl or substituted or unsubstituted C3-C12The carbocycle is a saturated or unsaturated ring, and the heterocycle is a saturated or unsaturated ring;
preferably, R1-R14Independently of one another, from the group consisting of hydrogen, deuterium, halogen, methyl, ethyl, propyl, n-butyl, tert-butyl, trifluoromethyl, cyano, phenyl, biphenyl, terphenyl, pentalenyl, indenyl, naphthyl, azulenyl, heptalenyl, adamantyl, bornyl, triphenylene, indacenyl, acenaphthenyl, fluorenyl, spirobifluorenyl, benzofluorenyl, dibenzofluorenyl, phenalenyl, phenanthrenyl, anthracenyl, fluoranthryl, benzophenanthrenyl, pyrenyl, chrysenyl, tetracenyl, picenyl, perylenyl, pentylphenyl, pentacenyl, rubinyl, coronenyl, ovaphenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, thienyl, furyl, quinolyl, carbazolyl, pyranyl, thiopyranyl, phthalazinyl, phenazinyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, indolyl, indolocarbazolyl, phenanthridinyl, acridinyl, terphenyl, phenanthridinyl, phenanthrenyl, perimidine, pteridinyl, quinazolinyl, quinoxalinyl, cinnolinyl, phenanthroline, carbolinyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, dinaphthofuranyl, benzocarbazolyl, dibenzocarbazolyl, dibenzothiapyrrolyl, benzonaphthothiapyrrolyl, dinaphthothiazolyl, benzimidazolyl, imidazopyridinyl;
further, in the above-mentioned fused ring compound,
R1-R14independently of one another, from hydrogen, deuterium, halogen, methyl, ethyl, propyl, n-butyl, tert-butylButyl, trifluoromethyl, cyano, phenyl, biphenyl, terphenyl, naphthyl;
cyclo A, B, C, D, E is independently selected from phenyl, biphenyl, terphenyl, pentalenyl, indenyl, naphthyl, azulenyl, heptalenyl, adamantyl, bornyl, triphenylene, indacenyl, acenaphthenyl, fluorenyl, spiro-bifluorenyl, benzofluorenyl, dibenzofluorenyl, phenalenyl, phenanthrenyl, anthracenyl, anthryl, benzophenanthrenyl, pyrenyl, chrysenyl, tetracenyl, picenyl, perylenyl, pentylphenyl, pentacenyl, rubinyl, coronenyl, egg phenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, thienyl, furyl, quinolyl, carbazolyl, pyranyl, thiopyranyl, phthalazinyl, phenazinyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, indolyl, indolocarbazolyl, phenanthridinyl, acridinyl, perimidine, pteridinyl, quinazolinyl, quinoxalinyl, phenanthridinyl, cinnolinyl, phenanthroline, carboline, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, dinaphthofuranyl, benzocarbazolyl, dibenzocarbazolyl, dibenzothiapyrrolyl, benzonaphthothiapyrrolyl, dinaphthothiapyrrolyl, benzimidazolyl, imidazopyridinyl.
Further, the fused ring compound has a molecular structure represented by any one of the following:
in a second aspect, the present invention provides a process for producing the above-mentioned fused ring compound,
the synthesis steps of the compound shown in the formula (I) are as follows:
taking a compound shown in a formula (A) and a compound shown in a formula (B) as initial raw materials, and carrying out Suzuki coupling reaction to obtain an intermediate 1-A; carrying out coupling reaction on the intermediate 1-A and a compound shown as a formula (C) to obtain an intermediate 2-A; carrying out coupling reaction on the intermediate 2-A and a compound shown as a formula (D) to obtain an intermediate 3-A; carrying out coupling and ring-closing reaction on the intermediate 3-A to obtain an intermediate 4-A; carrying out nitro reduction and ring closure reaction on the intermediate 4-A to obtain an intermediate 5-A; carrying out coupling reaction on the intermediate 5-A and a compound shown as a formula (E) to obtain a compound shown as a formula (I);
the synthetic route of the compound shown in the formula (I) is shown as follows:
the synthesis steps of the compound shown in the formula (II) are as follows:
taking a compound shown in a formula (F) and a compound shown in a formula (G) as initial raw materials, and carrying out Suzuki coupling reaction to obtain an intermediate 1-B; carrying out coupling reaction on the intermediate 1-B and a compound shown as a formula (H) to obtain an intermediate 2-B; carrying out coupling reaction on the intermediate 2-B and a compound shown as a formula (J) to obtain an intermediate 3-B; the intermediate 3-B is subjected to coupling ring-closing reaction to obtain an intermediate 4-B; carrying out nitro reduction and ring closure reaction on the intermediate 4-B to obtain an intermediate 5-B; carrying out coupling reaction on the intermediate 5-B and a compound shown as a formula (K) to obtain a compound shown as a formula (II);
the synthetic route of the compound shown in the formula (II) is shown as follows:
in a third aspect, the present invention provides an electronic device comprising a substrate, a first electrode formed on the substrate, a second electrode, an organic layer disposed between the first electrode and the second electrode, the organic layer comprising the above-described fused ring compound;
the organic layer comprises a luminescent layer, and at least one of a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole blocking layer and an electron blocking layer;
the light-emitting layer includes a host material containing the above-described fused ring compound and a dopant material.
In a fourth aspect, the present invention provides a display device comprising the above electronic device.
In a fifth aspect, the present invention provides a lighting device comprising the above electronic device.
The technical scheme of the invention has the following advantages:
1. the fused ring compound provided by the invention has a structure shown as a formula (I) or a formula (II), and the HOMO energy level of the fused ring compound is distributed in
2. The fused ring compound provided by the invention has larger molecular structure size and better intramolecular conjugation, so that the fused ring compound has better thermal stability, can avoid the material from being heated and decomposed in the process of film formation or use, avoids the loss of the function of a material layer, and improves the luminous efficiency and luminous performance of a device.
3. The fused ring compound provided by the invention has a three-dimensional structure, molecules cannot be stacked, energy transfer caused by molecular stacking can be avoided, generation of high-energy excitons can be avoided, and annihilation caused by the existence of the high-energy excitons can be effectively reduced.
4. The preparation method of the fused ring compound provided by the invention has the advantages of easily obtained starting materials, mild reaction conditions and simple operation steps, and provides a simple and easily-realized preparation method for large-scale production and application of the fused ring compound.
5. The condensed ring compound is used as a luminescent material, has excellent thermal stability, has LOMO and LUMO energy levels which can be matched with adjacent layers, has small driving voltage, can avoid exciton annihilation caused by molecular stacking, and is high in luminescent efficiency and long in service life.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph showing the theoretical calculation results of the HOMO level, LOMO level and energy band gap Eg of compound 13 in example 13 of the present invention;
FIG. 2 is a schematic view of the structures of organic electroluminescent devices in examples 27 to 52 of the present invention and comparative example 1.
Description of reference numerals:
1-substrate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-luminescent layer, 6-electron transport layer, 7-electron injection layer, 8-cathode.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "first", "second", and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims. In the drawings, the size and relative sizes of layers and regions may be exaggerated for clarity. It will be understood that when an element such as a layer is referred to as being "formed on" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly formed on" or "directly disposed on" another element, there are no intervening elements present.
Aryl-as used herein, is a non-fused or fused system.
Heteroaryl-as used herein, comprises at least one atom of N, O, S, P, Si, B, which may be one atom or a plurality of different atoms; the ring may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, or the like; the ring may be monocyclic, spiro or fused.