CN115557999A - Composition, preparation, organic electroluminescent device and display or lighting device - Google Patents

Composition, preparation, organic electroluminescent device and display or lighting device Download PDF

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CN115557999A
CN115557999A CN202211242176.9A CN202211242176A CN115557999A CN 115557999 A CN115557999 A CN 115557999A CN 202211242176 A CN202211242176 A CN 202211242176A CN 115557999 A CN115557999 A CN 115557999A
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杨云芳
豆利杰
王霞
佘远斌
李贵杰
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Zhejiang University of Technology ZJUT
Zhejiang Huadisplay Optoelectronics Co Ltd
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Zhejiang Huadisplay Optoelectronics Co Ltd
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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Abstract

The invention relates to a complex, an organic electroluminescent device and a display or lighting device. The phosphorescent material and the composition have good chemical stability, can balance the transport of holes and electrons, and have more efficient energy transmission between a host and an object.

Description

Composition, preparation, organic electroluminescent device and display or lighting device
Technical Field
The invention belongs to the field of organic electroluminescence, and particularly relates to a composition, a preparation, an organic electroluminescent device and a display or lighting device, wherein an object is a quadridentate ring metal platinum (II) complex phosphorescent material based on a carbazole derivative.
Background
Organic Light-Emitting diodes (OLEDs) are a new generation of full-color display and illumination technologies. Compared with the defects of low response speed, small visual angle, backlight source requirement, high energy consumption and the like of liquid crystal display, the OLED is used as an autonomous light-emitting device, does not need the backlight source and saves energy; the driving voltage is low, the response speed is high, the resolution and the contrast ratio are high, the visual angle is wide, and the low-temperature performance is outstanding; the OLED device can be made thinner and can be made into flexible structures. In addition, the method also has the advantages of low production cost, simple production process, large-area production and the like. Therefore, the OLED has wide and huge application prospect in the aspects of high-end electronic products and aerospace; with the gradual increase of investment, further development and upgrading of production equipment, OLEDs have a very wide application scene and development prospect in the future.
The core of the development of OLEDs is the design and development of light emitting materials. In early OLED devices, the light-emitting material was mainly organic small molecule fluorescent material. Spin statistical quantum, however, indicates that in the case of electroluminescence, singlet excitons and triplet excitons (exiton) are generated in 25% and 75%, respectively, and since conventional fluorescent materials can only utilize excitons in the singlet state, the maximum theoretical internal quantum efficiency is only 25%, and the remaining 75% of triplet excitons are lost by nonradiative transition. The Forrest professor at Prolington university, USA, and Thompson at southern California university, teach 1998 to find the phenomenon of phosphorescence electroluminescence of heavy metal organic complex molecules at room temperature. Due to the strong spin-orbit coupling effect of heavy metal atoms, excitons can be more easily subjected to intersystem crossing (ISC) from singlet states to triplet states, so that the OLED device can fully utilize all singlet states and triplet states excitons generated by electric excitation, and the theoretical internal quantum efficiency of the luminescent material can reach 100% (Nature, 1998,395,151).
The light-emitting layer in the currently applied OLED device almost completely uses a host-guest light-emitting system mechanism, namely, a guest light-emitting material is doped in a subject material, the energy system of the subject material is generally larger than that of the guest light-emitting material, and the energy is transferred from the host material to the guest material, so that the guest material is excited to emit light. Commonly used organic phosphorescent guest materials are typically heavy metal atoms such as iridium (III), platinum (II), pd (II), and the like. Currently applied heavy metal phosphorescent organic complex molecular cyclometalated iridium (III) complexMolecular, and limited in number. The content of metal platinum element in the earth crust and the annual output worldwide are about ten times of metal iridium element, and the IrCl used for preparing iridium (III) complex phosphorescent material 3 ·H 2 The price of O (1100 RMB/g) is much higher than that of PtCl for preparing platinum (II) complex phosphorescent material 2 (210 renminbi/gram); in addition, the preparation of the iridium (III) complex phosphorescent material relates to four-step reaction comprising iridium (III) dimer, iridium (III) intermediate ligand exchange, mer-iridium (III) complex synthesis and mer-to fac-iridium (III) complex isomer conversion, so that the total yield is greatly reduced, and the raw material IrCl is greatly reduced 3 ·H 2 The utilization rate of O improves the preparation cost of the iridium (III) complex phosphorescent material. In contrast, the preparation of the platinum (II) complex phosphorescent material only has the reaction of platinum salt in the final step of ligand metallization design, the utilization rate of platinum elements is high, and the preparation cost of the platinum (II) complex phosphorescent material can be further reduced. In summary, the preparation cost of the platinum (II) complex phosphorescent material is far lower than that of the iridium (III) complex phosphorescent material. However, the development of platinum and palladium complex materials and devices still has some technical difficulties, and how to improve the efficiency and the service life of the devices is an important research problem. There is therefore a great need to develop novel phosphorescent metal platinum (II) complexes.
At present, almost all light emitting layers in an organic OLED module use a host-guest light emitting system mechanism, that is, a guest light emitting material is doped in a host material, and generally, the energy system of the organic host material is larger than that of the guest material, that is, the energy is transferred from the host to the guest, so that the guest material is excited to emit light. A commonly used phosphorescent organic material CBP (4,4' -bis (9-carbazolyl) -biphenyl) has a high efficiency and high triplet energy level, which can be efficiently transferred from a light emitting organic material to a guest phosphorescent light emitting material when it is used as an organic material. However, due to the characteristic that holes of CBP are easily transported and electrons are hardly flowed, the charges of the light emitting layer are not balanced, and as a result, the efficiency of the device is lowered.
Disclosure of Invention
The invention aims to provide one or more guest phosphorescent materials and host materials applied to a light emitting layer of an organic electroluminescent device, a combination of the guest phosphorescent materials and the host materials, and the organic electroluminescent device comprising the combination. The invention finds that the combination of the specific host material and the guest phosphorescent material can improve the external quantum efficiency of the organic electroluminescent device and reduce the operating voltage of the device.
The invention provides one or more tetradentate cyclometalated platinum (II) complex guest phosphorescent materials based on carbazole-pyridine derivatives, which are represented by structural formulas (I-1) and (I-2):
Figure BDA0003883681400000021
wherein:
m is Pt; y is 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 、Y 8 、Y 9 、Y 10 、Y 11 、Y 12 、Y 13 、Y 14 、Y 15 、Y 16 、Y 17 、Y 18 、Y 19 And Y 20 Each independently is N or CH; r is 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents mono-, di-, tri-or unsubstituted; r 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxyl group, a hydrazine group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, an alkylsilyl group, a substituted or unsubstituted arylsilyl groupAnd two or more adjacent R are any one of a substituted or unsubstituted aryloxysilyl group, a substituted or unsubstituted heteroaryloxysilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroarylacyl group, a substituted or unsubstituted phosphinyl group 1 、R 2 、R 3 、R 4 、R 5 And R 6 May be selectively linked to form fused rings.
In another aspect, the present invention provides a combination of one or more tetradentate cyclometalated platinum (II) complex guest phosphorescent materials based on carbazole-pyridine derivatives represented by structural formulae (I-1) and (I-2), and one or more host materials represented by structural formulae (II) or (III), the structural formulae (I) and (II) or (III) being as follows:
Figure BDA0003883681400000022
Figure BDA0003883681400000031
wherein:
in the formulae (I-1) and (I-2), M is Pt; y is 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 、Y 8 、Y 9 、Y 10 、Y 11 、Y 12 、Y 13 、Y 14 、Y 15 、Y 16 、Y 17 、Y 18 、Y 19 And Y 20 Each independently is N or CH; r 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents mono-, di-, tri-or unsubstituted; r 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents hydrogen, deuterium, alkyl, haloalkyl, cycloalkyl, alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryloxy, halogen, cycloalkenyl, substitutedOr any one of an unsubstituted heterocyclic group, alkenyl group, alkynyl group, hydroxyl group, mercapto group, nitro group, cyano group, substituted or unsubstituted amino group, mono-or dialkylamino group, mono-or diarylamino group, ester group, nitrile group, isonitrile group, alkoxycarbonyl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, sulfinyl group, ureido group, phosphonamido group, imino group, sulfo group, carboxyl group, hydrazine group, substituted or unsubstituted arylamino group, substituted or unsubstituted heteroarylamino group, alkylsilyl group, substituted or unsubstituted arylsilyl group, substituted or unsubstituted heteroarylsilyl group, substituted or unsubstituted aryloxysilyl group, substituted or unsubstituted heteroaryloxy group, substituted or unsubstituted aryloxysilyl group, and two or more adjacent R groups 1 、R 2 、R 3 、R 4 、R 5 And R 6 May be optionally linked to form fused rings;
in the formulae (II) and (III), X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 、X 12 、X 13 、X 14 、X 15 、X 16 、X 17 、X 18 、X 19 And X 20 Each independently is N or CH; z 1 、Z 2 、Z 3 、Z 4 、Z 5 、Z 6 、Z 7 、Z 8 、Z 9 、Z 10 、Z 11 、Z 12 And Z 13 Each independently is N or CH, and at least 2 are N; l is 1 、L 2 And L 3 Absent or selected from single bonds, O, S, CR 15 R 16 、SiR 17 R 18 、NR 19 (ii) a A. B, C and D are each independently selected from C6-C30 aryl, C2-C30 heteroaryl; r 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R 19 Each independently represents mono-, di-, tri-, tetra-, or unsubstituted; and R is 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R 19 Each independently represents any one of hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxyl group, a hydrazino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, an alkylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroaryloxy group, and two or more adjacent R groups 1 、R 2 、R 3 、R 4 、R 5 And R 6 May be selectively linked to form fused rings.
Further, the tetradentate cyclometalated platinum (II) complex guest phosphorescent material based on coordination of carbazole derivatives has a structure of one of the following:
Figure BDA0003883681400000041
Figure BDA0003883681400000051
Figure BDA0003883681400000061
Figure BDA0003883681400000071
Figure BDA0003883681400000081
Figure BDA0003883681400000091
Figure BDA0003883681400000101
Figure BDA0003883681400000111
Figure BDA0003883681400000121
Figure BDA0003883681400000131
Figure BDA0003883681400000141
Figure BDA0003883681400000151
Figure BDA0003883681400000161
Figure BDA0003883681400000171
Figure BDA0003883681400000181
Figure BDA0003883681400000191
Figure BDA0003883681400000201
Figure BDA0003883681400000211
Figure BDA0003883681400000221
further, the organic host material has a formula (II) selected from the compounds described in (II) -1 to (II) -24:
Figure BDA0003883681400000231
Figure BDA0003883681400000241
wherein, X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 And X 10 ，L 1 、L 2 And L 3 A and B, R 7 、R 8 、R 9 And R 10 And the above definitionsThe same is true.
Further, wherein A, B, C and D are selected from the group described by the following structure:
Figure BDA0003883681400000242
wherein R is 15 、R 16 、R 17 、R 18 And R 19 As defined above.
Further, the host material of the present invention is selected from the following structures or a group consisting of the following structures:
Figure BDA0003883681400000251
Figure BDA0003883681400000261
Figure BDA0003883681400000271
Figure BDA0003883681400000281
Figure BDA0003883681400000291
Figure BDA0003883681400000301
Figure BDA0003883681400000311
Figure BDA0003883681400000321
Figure BDA0003883681400000331
Figure BDA0003883681400000341
Figure BDA0003883681400000351
Figure BDA0003883681400000361
Figure BDA0003883681400000371
Figure BDA0003883681400000381
Figure BDA0003883681400000391
Figure BDA0003883681400000401
Figure BDA0003883681400000411
Figure BDA0003883681400000421
Figure BDA0003883681400000431
Figure BDA0003883681400000441
Figure BDA0003883681400000451
Figure BDA0003883681400000461
Figure BDA0003883681400000471
Figure BDA0003883681400000481
Figure BDA0003883681400000491
Figure BDA0003883681400000501
Figure BDA0003883681400000511
Figure BDA0003883681400000521
Figure BDA0003883681400000531
Figure BDA0003883681400000541
Figure BDA0003883681400000551
Figure BDA0003883681400000561
Figure BDA0003883681400000571
Figure BDA0003883681400000581
Figure BDA0003883681400000591
Figure BDA0003883681400000601
Figure BDA0003883681400000611
Figure BDA0003883681400000621
Figure BDA0003883681400000631
Figure BDA0003883681400000641
Figure BDA0003883681400000651
Figure BDA0003883681400000661
Figure BDA0003883681400000671
Figure BDA0003883681400000681
Figure BDA0003883681400000691
Figure BDA0003883681400000701
Figure BDA0003883681400000711
Figure BDA0003883681400000721
Figure BDA0003883681400000731
Figure BDA0003883681400000741
Figure BDA0003883681400000751
Figure BDA0003883681400000761
Figure BDA0003883681400000771
Figure BDA0003883681400000781
Figure BDA0003883681400000791
Figure BDA0003883681400000801
Figure BDA0003883681400000811
Figure BDA0003883681400000821
Figure BDA0003883681400000831
Figure BDA0003883681400000841
preferably, the host material of the present invention is selected from the following structures or a group consisting of the following structures:
Figure BDA0003883681400000851
Figure BDA0003883681400000861
Figure BDA0003883681400000871
Figure BDA0003883681400000881
the invention also relates to an organic electroluminescent device comprising a cathode layer, an anode layer and an organic layer, wherein the organic layer comprises at least one of a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron injection layer and an electron transport layer, and the light-emitting layer of the device contains one or more guest compounds represented by formula (I) and one or more host compounds represented by formula (II) or formula (III).
The mass percentage of the guest material in the organic electroluminescent device luminescent layer composition is 0.1-50%.
When the combination of two compounds selected from the structural formula (II) or the structural formula (III) is used as a main material, the volume ratio of the two compounds is 1.
The present invention relates to a composition comprising a formulation of one or more of the structural formulae (I) and (II) or (III) with a solvent, the solvent used is not particularly limited, and unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decahydronaphthalene, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane and the like, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene and the like, ether solvents such as tetrahydrofuran, tetrahydropyran and the like, ester solvents such as alkyl benzoate and the like, which are well known to those skilled in the art can be used.
The invention also provides an organic electroluminescent device which comprises a cathode layer, an anode layer and an organic layer, wherein the organic layer comprises a composition, the composition comprises a tetracyclic metal platinum (II) complex phosphorescent material based on carbazole derivatives and an organic host material, and the structural formula of the metal platinum (II) complex phosphorescent material is shown as formulas (I-1) and (I-2); the organic host material has a structural formula (II) or (III):
Figure BDA0003883681400000882
Figure BDA0003883681400000891
wherein:
in the formulae (I-1) and (I-2), M is Pt; y is 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 、Y 8 、Y 9 、Y 10 、Y 11 、Y 12 、Y 13 、Y 14 、Y 15 、Y 16 、Y 17 And Y 18 、Y 19 And Y 20 Each independently is N or CH; r 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents mono-, di-, tri-or no substitution; r 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkyl groupAny one of oxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted or unsubstituted arylamino, substituted or unsubstituted heteroarylamino, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted aryloxysilyl, substituted or unsubstituted heteroaryloxysilyl, substituted or unsubstituted arylacyl, substituted or unsubstituted heteroarylacyl, substituted or unsubstituted phosphinyl, and two or more adjacent R' s 1 、R 2 、R 3 、R 4 、R 5 And R 6 May be optionally linked to form fused rings;
in the formulae (II) and (III), X 1 、X 2 、X 3 、X 4 、X3 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 、X 12 、X 13 、X 14 、X 15 、X 16 、X 17 、X 18 、X 19 And X 20 Each independently is N or CH; z 1 、Z 2 、Z 3 、Z 4 、Z 5 、Z 6 、Z 7 、Z 8 、Z 9 、Z 10 、Z 11 、Z 12 And Z 13 Each independently is N or CH, and at least 2 are N; l is a radical of an alcohol 1 、L 2 And L 3 Absent or selected from single bonds, O, S, CR 15 R 16 、SiR 17 R 18 、NR 19 (ii) a A. B, C and D are each independently selected from C6-C30 aryl, C2-C30 heteroaryl; r 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R 19 Each independently represents mono-, di-, tri-, tetra-, or unsubstituted; and R is 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R 19 Each independently represents any one of hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxyl group, a hydrazino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, an alkylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroaryloxy group, and two or more adjacent R groups 1 、R 2 、R 3 、R 4 、R 5 And R 6 May be selectively linked to form fused rings.
Preferably, the platinum (II) complex is any one of the compound Pt1 to the compound Pt 532.
Preferably, the above formula (II) is selected from the group consisting of compounds described by (II) -1 to (II) -24:
Figure BDA0003883681400000901
Figure BDA0003883681400000911
wherein, X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 And X 10 ，L 1 、L 2 And L 3 A and B, R 7 、R 8 、R 9 And R 10 As defined above.
Preferably, A, B, C and D in the above formula are selected from the group described by the following structures:
Figure BDA0003883681400000912
wherein R15, R16, R17, R18 and R19 are as defined above.
Preferably, the organic host material of formula (II) or formula (III) is selected from compounds 0-1 to compounds 33-80 described above.
The invention also provides a display or lighting device which comprises the organic electroluminescent device.
The invention also provides application of the quadridentate ring metal platinum (II) complex phosphorescent material containing the carbazole derivative in manufacturing an organic light-emitting device.
The present invention is not particularly limited to the method for preparing the organic electroluminescent device, and may be prepared using a method and materials for preparing a light emitting device well known to those skilled in the art, except for using one or more guest compounds represented by structural formula I and one or more host compounds represented by structural formula (II) or (III).
The Organic electroluminescent device of the present invention is any one of an Organic photovoltaic device, an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic paper (e-paper), an Organic Photoreceptor (OPC), an Organic Thin Film Transistor (OTFT), an Organic Memory device (Organic Memory Element), a lighting device, and a display device.
In the present invention, the organic photoelectric device is an anode which can be formed by depositing a metal or an oxide having conductivity and an alloy thereof on a substrate by a sputtering method, electron beam evaporation, vacuum evaporation, or the like; and sequentially evaporating a hole injection layer, a hole transport layer, a luminescent layer, an air barrier layer and an electron transport layer on the surface of the prepared anode, and then evaporating a cathode. The organic electroluminescent device is prepared by vapor deposition of the cathode, the organic layer and the anode on the substrate except the above method. The organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer. In the invention, the organic layer is prepared by adopting a high polymer material according to a solvent engineering (spin-coating), tape-casting (tape-casting), doctor-blading (sector-Printing), screen-Printing (Screen-Printing), ink-jet Printing or Thermal-Imaging (Thermal-Imaging) method instead of an evaporation method, so that the number of the layers of the device can be reduced.
The materials used for the organic electroluminescent device according to the present invention may be classified as top emission, low emission, or double-sided emission. The compound of the organic electroluminescent device according to the embodiment of the present invention can be applied to the aspects of the organic solar cell, the lighting OLED, the flexible OLED, the organic photoreceptor, the organic thin film transistor and other electroluminescent devices by using the similar principle of the organic light emitting device.
The invention has the beneficial effects that: guest platinum (II) phosphorescent material molecules based on two bidentate ligands are prone to vibration and distortion resulting in non-radiative decay, making the phosphorescent efficiency low. Compared with bidentate platinum (II) complexes, the rigid structure of the tetradentate ring metal platinum (II) complex guest phosphorescent material based on carbazole-pyridine-carbazole-pyridine or carbazole-pyridine-benzene ring-pyridine can effectively inhibit non-radiative decay caused by molecular vibration, so that high-efficiency luminescence can be realized, and the tetradentate ring metal platinum (II) complex guest phosphorescent material has good chemical stability; in addition, the host material composition has good thermal stability, and the transport of holes and electrons can be balanced by the host material composition, so that the energy transmission between a host and an object is more efficient.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
FIG. 1 is a room temperature emission spectrum of a platinum complex Pt1 in a dichloromethane solution in an embodiment;
FIG. 2 is a room temperature emission spectrum of a platinum complex Pt2 in a dichloromethane solution in an embodiment;
FIG. 3 is a room temperature emission spectrum of a platinum complex Pt3 in a dichloromethane solution in an embodiment;
FIG. 4 is a HOMO and LUMO orbital distribution and energy level comparison of Pt1, pt2, pt3, and Pt4 calculated by Density Functional Theory (DFT);
FIG. 5 is a comparison of HOMO and LUMO orbital distributions and energy levels thereof for Pt16, pt65, pt67, and Pt68 calculated by Density Functional Theory (DFT);
FIG. 6 is a HOMO and LUMO orbital distribution and energy level comparison of Pt529, pt530, pt531 and Pt532 calculated by Density Functional Theory (DFT);
fig. 7 is a structural diagram of an organic electroluminescent diode device according to the present invention, in which 110 denotes a substrate, 120 denotes an anode, 130 denotes a hole injection layer, 140 denotes a hole transport layer, 150 denotes a light emitting layer, 160 denotes a hole blocking layer, 170 denotes an electron transport layer, 180 denotes an electron injection layer, and 190 denotes a cathode.
Detailed Description
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.
The disclosure may be understood more readily by reference to the following detailed description and the examples included therein.
Before the present compounds, devices, and/or methods are disclosed and described, it is to be understood that they are not limited to the particular synthetic methods (otherwise specified), or to the particular reagents (otherwise specified), as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing, the exemplary methods and materials are described below.
In a preferred embodiment of the present invention, the OLED device according to the invention comprises a hole transport layer, which may preferably be selected from known or unknown materials, particularly preferably from the following structures, without representing the present invention being limited to the following structures:
Figure BDA0003883681400000931
in a preferred embodiment of the present invention, the hole transport layer contained in the OLED device of the present invention comprises one or more p-type dopants. Preferred p-type dopants of the present invention are, but do not represent a limitation of the present invention to:
Figure BDA0003883681400000932
Figure BDA0003883681400000941
in a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of the compounds ET-1 to ET-13, but does not represent that the present invention is limited to the following structures:
Figure BDA0003883681400000942
the term "optional" or "optionally" as used herein means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
Disclosed are components useful in preparing the compositions described herein, as well as the compositions themselves to be used in the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds may not be specifically disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules comprising the compound are discussed, then various and each combination and permutation of the compound are specifically contemplated and may be made, otherwise specifically indicated to the contrary. Thus, if a class of molecules A, B and C and a class of molecules D, E and F are disclosed, and examples of combination molecules a-D are disclosed, then even if each is not separately recited, it is contemplated that each separately and collectively contemplated meaning combination is disclosed, a-E, A-F, B-D, B-E, B-F, C-D, C-E and C-F. Likewise, any subset or combination of these is also disclosed. Thus, for example, it is contemplated that groups A-E, B-F and C-E are disclosed. These concepts are applicable to all aspects of the invention, including but not limited to the steps of the methods of making and using the compositions. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with a specific embodiment or combination of embodiments of the method.
The linking atom used in the present invention can link two groups, for example, N and C groups. The linking atom can optionally (if valency permits) have other attached chemical moieties. For example, in one aspect, oxygen does not have any other chemical group attached because once bonded to two atoms (e.g., N or C) valences have been satisfied. Conversely, when carbon is a linking atom, two additional chemical moieties can be attached to the carbon atom. Suitable chemical moieties include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, = O, halogen, nitro, amine, amide, mercapto, aryl, heteroaryl, cycloalkyl, and heterocyclyl.
The term "cyclic structure" or similar terms as used herein refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.
The term "substituted" as used herein is intended to encompass all permissible substituents of organic compounds. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents for appropriate organic compounds can be one or more, the same or different. For the purposes of the present invention, a heteroatom (e.g. nitrogen) can have a hydrogen substituent and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatom. The present disclosure is not intended to be limited in any way by the permissible substituents of organic compounds. Likewise, the term "substituted" or "substituted with" includes the implicit proviso that such substitution is consistent with the atom being substituted and the allowed valence of the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.)). It is also contemplated that, in certain aspects, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted), unless explicitly stated to the contrary.
In defining the terms, "R 1 ”、“R 2 ”、“R 3 "and" R 4 "used as a general symbol in the present invention denotes various specific substituents. These symbols can be any substituent, are not limited to those disclosed herein, and when they are defined as certain substituents in one instance, they can be defined as some other substituents in other instances.
The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, half-yl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, halo, hydroxy, nitro, silyl, sulfo-oxo (Sulfo-oxo), or thiol as described herein. A "lower alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms.
Throughout the specification, "alkyl" is generally used to refer to both unsubstituted alkyl and substituted alkyl; however, substituted alkyl groups are also specifically mentioned in the present invention by identifying specific substituents on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl group substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below, and the like. When "alkyl" is used in one instance and a specific term such as "alkyl alcohol" is used in another instance, it is not meant to imply that the term "alkyl" does not refer to the specific term such as "alkyl alcohol" or the like at the same time.
This practice is also applicable to the other groups described in the present invention. That is, when a term such as "cycloalkyl" refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moiety can be otherwise specifically identified in the present invention; for example, a specifically substituted cycloalkyl group can be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy group may be specifically referred to as, for example, "halogenated alkoxy", and a specific substituted alkenyl group may be, for example, "enol" and the like. Likewise, practice of using general terms such as "cycloalkyl" and specific terms such as "alkylcycloalkyl" is not intended to imply that the general terms do not also encompass the specific terms.
The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring made up of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like. The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above and is included within the meaning of the term "cycloalkyl" in which at least one ring carbon atom is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur or phosphorus. The cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, halo, hydroxy, nitro, silyl, sulfo-oxo, or thiol as described herein.
The term "polyalkylene group" as used herein refers to a group containing two or more CH groups 2 Groups and other moieties that are the same are attached. "polyalkylene group" may be represented by- (CH) 2 ) a -, wherein "a" is an integer of 2 to 500.
The terms "alkoxy" and "alkoxy group," as used herein, refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, "alkoxy" may be defined as-OR 1 Wherein R is 1 Is alkyl or cycloalkyl as defined above. "alkoxy" also includes polymers of alkoxy groups as just described; that is, the alkoxy group may be a polyether such as-OR 1 -OR 2 OR-OR 1 -(OR 2 ) a -OR 3 Wherein "a" is an integer of 1 to 200, and R 1 、R 2 And R 3 Each independently an alkyl group, a cycloalkyl group, or a combination thereof.
The term "alkenyl" as used herein is a hydrocarbon group of 2 to 30 carbon atoms, the structural formula of which contains at least one carbon-carbon double bond. Asymmetric structures such as (R) 1 R 2 )C＝C(R 3 R 4 ) Intended to include both the E and Z isomers. This can be presumed in the structural formula of the present invention, in which an asymmetric olefin is present, or it can be explicitly represented by the bond symbol C = C. The alkenyl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxy, carbonyl, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.
The term "cycloalkenyl" as used herein is a non-aromatic carbon-based ring, consisting of at least 3 carbon atoms and containing at least one carbon-carbon double bond, i.e., C = C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl" is a type of cycloalkenyl group as defined above, and is included within the meaning of the term "cycloalkenyl", where at least one carbon atom of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.
The term "alkynyl" as used herein is a hydrocarbon group having 2 to 30 carbon atoms having a structural formula containing at least one carbon-carbon triple bond. Alkynyl groups can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.
The term "cycloalkynyl" as used herein is a non-aromatic, carbon-based ring containing at least seven carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term "heterocycloalkynyl" is a type of cycloalkenyl group as defined above and is included within the meaning of the term "cycloalkynyl" wherein at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.
The term "aryl" as used herein is a group containing any carbon-based aromatic group including, but not limited to, phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracenyl, phenanthrenyl, and the like. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group that contains an aromatic group, which does not contain heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups joined together via a fused ring structure, as in naphthalene, or two aryl groups connected via one or more carbon-carbon bonds, as in biphenyl.
The term "aldehyde" as used herein is represented by the formula-C (O) H. Throughout the specification, "C (O)" is an abbreviated form of carbonyl (i.e., C = O).
The term "amine" or "amino" as used herein is defined by the formula-NR 1 R 2 Is represented by the formula (I) in which R 1 And R 2 Can be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl.
The term "alkylamino" as used herein is represented by the formula-NH (-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl) amino, (tert-butyl) amino, pentylamino, isopentylamino, (tert-pentyl) amino, hexylamino, and the like.
The term "dialkylamino" as used herein is defined by the formula-N (alkyl) 2 Wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di (sec-butyl) amino, di (tert-butyl) amino, dipentylamino, diisopentylamino, di (tert-pentyl) amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.
The term "carboxylic acid" as used herein is represented by the formula-C (O) OH.
The term "ester" as used herein is defined by the formula-OC (O) R 1 OR-C (O) OR 1 Is represented by the formula wherein R 1 May be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein. The term "polyester" as used herein is defined by the formula- (R) 1 O(O)C-R 2 -C(O)O) a -or- (R) 1 O(O)C-R 2 -OC(O)) a -represents wherein R 1 And R 2 May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and "a" is an integer from 1 to 500. The term "polyester" is used to describe a group produced by the reaction between a compound having at least two carboxyl groups and a compound having at least two hydroxyl groups.
The term "ether" as used herein is defined by the formula R 1 OR 2 Is represented by the formula (I) in which R 1 And R 2 May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein. The term "polyether" as used herein is defined by the formula- (R) 1 O-R 2 O) a -represents wherein R 1 And R 2 May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.
The term "halogen" as used herein refers to the halogens fluorine, chlorine, bromine and iodine.
The term "heterocyclyl" as used herein refers to monocyclic and polycyclic non-aromatic ring systems of 3 to 30 carbon atoms, and "heteroaryl" as used herein refers to monocyclic and polycyclic aromatic ring systems of no more than 60 carbon atoms: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl including 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl and 1,3,4-oxadiazolyl, piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrazinyl including 1,2,4,5-tetrazinyl, tetrazolyl including 1,2,3,4-tetrazolyl and 1,2,4,5-tetrazolyl, thiadiazolyl including 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl and 1,3,4-thiadiazolyl, thiazolyl, thienyl, triazolyl including 1,3,5-triazinyl and 3638 xzft 3638-triazinyl, triazolyl including 3724-zxft 3724-4924-triazolyl, and the like.
The term "hydroxy" as used herein is represented by the formula-OH.
The term "ketone" as used herein is defined by the formula R 1 C(O)R 2 Is represented by the formula (I) in which R 1 And R 2 May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term "azido" as used herein is of the formula-N 3 And (4) showing.
The term "nitro" as used herein is of the formula-NO 2 And (4) showing.
The term "nitrile" as used herein is represented by the formula-CN.
The term "silyl" as used herein, is defined by the formula-SiR 1 R 2 R 3 Is represented by the formula (I) in which R 1 、R 2 And R 3 And may independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein.
The term "thio-oxo" as used herein is defined by the formula-S (O) R 1 、-S(O) 2 R 1 、-OS(O) 2 R 1 or-OS (O) 2 OR 1 Is represented by the formula (I) in which R 1 May be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout the specification, "S (O)" is a shorthand form of S = O. The term "sulfonyl" as used herein refers to a compound of the formula-S (O) 2 R 1 A thio-oxo group of the formula, wherein R 1 Can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl. The term "sulfone" as used herein is defined by the formula R 1 S(O) 2 R 2 Is represented by the formula (I) in which R 1 And R 2 May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein. The term "sulfoxide" as used herein is defined by the formula R 1 S(O)R 2 Is represented by the formula (I) in which R 1 And R 2 May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group as described herein.
The term "mercapto" as used herein is represented by the formula-SH
"R" used in the present invention 1 ”、“R 2 ”、“R 3 ”、“R n "(wherein n is an integer) may independently have one or more of the groups listed above. For example, if R 1 Being a straight chain alkyl, then one hydrogen atom of the alkyl group may be optionally substituted with hydroxyl, alkoxy, alkyl, halogen, and the like. Depending on the choice of group, the first group may be incorporated within the second group, or alternatively, the first group may be suspendedPendant, i.e., attached to a second group. For example, for the phrase "alkyl group comprising an amino group," the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group may be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is intercalated or attached to the second group.
The compounds of the present invention may contain "optionally substituted" moieties. Generally, the term "substituted" (whether or not the term "optionally" is present above) means that one or more hydrogens of the indicated moiety are replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have suitable substituents at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituents at each position may be the same or different. The combinations of substituents contemplated by the present invention are preferably those that form stable or chemically feasible compounds. In certain aspects, it is also contemplated that each substituent may be further optionally substituted (i.e., further substituted or unsubstituted), unless clearly indicated to the contrary.
The term "fused ring" as used herein means that two adjacent substituents may be fused to form a six-membered aromatic ring, a heteroaromatic ring, such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a m-diazacyclo ring, etc., as well as a saturated six-or seven-membered carbocyclic or carbocyclic ring, etc.
The structure of the compound can be represented by the following formula:
Figure BDA0003883681400000981
it is understood to be equivalent to the following formula:
Figure BDA0003883681400000982
where n is typically an integer. Namely, R n Is understood to mean five individual substituents R a(1) 、R a(2) 、R a(3) 、R a(4) 、R a (5) . By "individual substituents" is meant that each R substituent can be independently defined. For example, if in one instance R a(m) Is halogen, then R in this case a(n) Not necessarily halogen.
R is referred to several times in the chemical structures and parts disclosed and described in this specification 1 、R 2 、R 3 、R 4 、R 5 、R 6 And the like. In the specification, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Etc. are each applicable to the citation of R 1 、R 2 、R 3 、R 4 、R 5 、R 6 Etc., unless otherwise specified.
The term "fused ring" as used herein means that two adjacent substituents may be fused to form a six-membered aromatic ring, a heteroaromatic ring, such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a m-diazacyclo ring, etc., as well as a saturated six-or seven-membered carbocyclic or carbocyclic ring, etc.
Optoelectronic devices using organic materials are becoming more and more stringent for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, and therefore organic photovoltaic devices have the potential for cost advantages of inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include Organic Light Emitting Devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength at which the organic light-emitting layer emits light can generally be tuned with appropriate dopants.
The excitons decay from the singlet excited state to the ground state to generate instant luminescence, which is fluorescence. If excitons decay from the triplet excited state to the ground state to generate light emission, it is phosphorescence. Phosphorescent metal complexes (e.g., platinum complexes) have shown their potential to utilize both singlet and triplet excitons, achieving 100% internal quantum efficiency, due to the strong spin-orbit coupling of heavy metal atoms between singlet and triplet excited states, effectively enhancing intersystem crossing (ISC). Accordingly, phosphorescent metal complexes are a good choice of dopants in the emissive layer of Organic Light Emitting Devices (OLEDs) and have gained great attention in both academic and industrial fields. Over the last decade, much effort has been made, resulting in profitable applications of this technology, for example, OLEDs have been used for advanced displays for smart phones, televisions and digital cameras.
However, blue electroluminescent devices remain the most challenging area in the art to date, and stability of blue devices is a big problem. The choice of host material has proven to be very important for the stability of blue devices. However, the triplet excited state (T1) minimum energy of the blue light emitting material is very high, which means that the triplet excited state (T1) minimum energy of the host material of the blue device should be higher. This results in increased difficulty in developing the host material for blue devices.
The metal complexes of the present invention can be tailored or tuned to specific applications where specific emission or absorption characteristics are desired. The optical properties of the disclosed metal complexes can be tuned by changing the structure of the ligands surrounding the metal center or by changing the structure of the fluorescent luminophores on the ligands. For example, metal complexes or electron-withdrawing substituents of ligands having electron-donating substituents may generally exhibit different optical properties in the emission and absorption spectra. The color of the metal complex can be adjusted by modifying the fluorescent emitter and the conjugated group on the ligand.
The emission of the complexes of the invention can be modulated, for example, by changing the ligand or fluorescent emitter structure, for example from ultraviolet to near infrared. Fluorescent emitters are a group of atoms in an organic molecule that can absorb energy to produce a singlet excited state, which rapidly decays to produce instant light emission. In one aspect, the complexes of the invention can provide emission in a large portion of the visible spectrum. In a specific example, the complex of the present invention can emit light in the wavelength band of visible light or near infrared light. On the other hand, the complexes of the invention have improved stability and efficiency relative to conventional emissive complexes. In addition, the complexes of the invention may be used as luminescent labels, for example, for biological applications, anticancer agents, emitters in Organic Light Emitting Diodes (OLEDs), or combinations thereof. In another aspect, the complexes of the present invention can be used in light emitting devices, such as Compact Fluorescent Lamps (CFLs), light Emitting Diodes (LEDs), incandescent lamps, and combinations thereof.
Disclosed herein are compounds or complex complexes comprising platinum. The terms compound or complex are used interchangeably herein. In addition, the compounds disclosed herein have a neutral charge.
The compounds disclosed herein may exhibit desirable properties and have emission and/or absorption spectra that can be tailored by selection of appropriate ligands. In another aspect, the invention can exclude any one or more of the compounds, structures, or portions thereof specifically recited herein.
The compounds disclosed herein are suitable for use in a wide variety of optical and electro-optical devices, including but not limited to light absorbing devices, such as solar and photosensitive devices, organic Light Emitting Diodes (OLEDs), light emitting devices or devices capable of compatible light absorption and emission and as labels for biological applications.
As mentioned above, the disclosed compounds are platinum complexes. At the same time, the compounds disclosed herein can be used as host materials for OLED applications, such as full color displays.
The compounds disclosed herein are useful in a variety of applications. As a light-emitting material, the compound is useful for organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.
In addition, the compounds of the present invention are used in light emitting devices (e.g., OLEDs) to improve the luminous efficiency and the operation time of the devices, relative to conventional materials.
The compounds of the present invention may be prepared using a variety of methods, including but not limited to those described in the examples provided herein.
The compounds disclosed herein may be delayed fluorescence and/or phosphorescence emitters. In one aspect, the compounds disclosed herein can be delayed fluorescence emitters. In one aspect, the compounds disclosed herein can be phosphorescent emitters. In another aspect, the compounds disclosed herein can be delayed fluorescence emitters and phosphorescence emitters.
The disclosed compounds are suitable for use in a variety of optical and electro-optical devices, including but not limited to light absorbing devices such as solar and light sensitive devices, organic Light Emitting Diodes (OLEDs), light emitting devices or devices having both light absorbing and light emitting capabilities, and as labels for biological applications.
The compounds provided by embodiments of the present invention may be used in a light emitting device, such as an OLED, comprising at least one cathode, at least one anode and at least one light emitting layer, at least one of which comprises the above-described phenylcarbazole-based tetradentate cyclometalated platinum complex. Specifically, the light emitting device may include an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode, which are sequentially deposited. The hole transport layer, the luminescent layer and the electron transport layer are all organic layers, and the anode and the cathode are electrically connected.
Synthetic examples
The following examples of compound syntheses, compositions, devices, or processes are intended to provide a general approach to the art, and are not intended to limit the scope of the patent. Unless otherwise indicated, the weighing was carried out separately, at ambient temperature, or at a pressure close to ambient.
The following examples provide methods for the preparation of the novel compounds, but the preparation of such compounds is not limited to this method. In this area of expertise, the compounds protected in this patent can be prepared by the methods listed below or by other methods, since they are easy to modify. The following examples are given by way of example only and are not intended to limit the scope of the patent. The temperature, catalyst, concentration, reactants, and course of reaction can all be varied to select different conditions for the preparation of the compound for different reactants.
1 H NMR(500MHz)、 1 H NMR(400MHz)、 13 C NMR (126 MHz) spectra were determined on an ANANCE III (500M) model NMR spectrometer; unless otherwise stated, nuclear magnetic resonance is carried out by using DMSO-d 6 Or CDCl containing 0.1% 3 As a solvent, wherein 1 H NMR spectrum if CDCl 3 As solvent, TMS (δ =0.00 ppm) was used as internal standard; in DMSO-d 6 As solvent, TMS (δ =0.00 ppm) or residual DMSO peak (δ =2.50 ppm) or residual water peak (δ =3.33 ppm) was used as internal standard. 13 In the C NMR spectrum, as CDCl 3 (delta =77.00 ppm) or DMSO-d 6 (δ =39.52 ppm) as an internal standard. Measuring on an HPLC-MS Agilent 6210TOF LC/MS type mass spectrometer; HRMS spectra were determined on an Agilent 6210TOF LC/MS liquid chromatography-time of flight mass spectrometer. 1 H NMR spectrum data: s = singlet, d = doubtet, t = triplet, q = quartz, p = quintet, m = multiplex, br = broad.
Synthetic route
Example 1: the platinum complex Pt1 can be synthesized by the following route:
Figure BDA0003883681400001001
synthesis of L1: to a 50mL three-necked flask with a magnetic rotor was added intermediate 4 (300mg, 0.69mmol,1.0 equiv.), M-1 (281mg, 0.76mmol,1.1 equiv.), K 2 CO 3 (238mg, 1.72mmol,2.5 equiv.), pd (PPh) 3 ) 4 (1695g, 0.0138mmol,0.02 eq), then the nitrogen is pumped three times, and 1,4-dioxane: H is added under the protection of nitrogen 2 O (10ml. The mixture was stirred in a 90 ℃ oil bath for 10 hours and thin layer chromatography monitored for completion of the reaction of starting material A and unreacted portion B. After cooling to room temperature, the reaction mixture was quenched with water, extracted three times with ethyl acetate and water, and the organic phases were combined and dried over anhydrous sodium sulfate. And (3) distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by using a silica gel chromatographic column, and eluting the eluent: petroleum ether/ethyl acetate =50, raw material B recovered 86mg back, finally yielding intermediate L1, 160mg of white solid, yield 54%.1H NMR (400MHz, DMSO). Delta.1.44 (s, 9H)),1.49(s,9H),7.31(d,J＝8.0,1H),7.34(ddd,J＝1.2,5.6,6.4Hz,1H),7.38(td,J＝0.8,8.0Hz,1H),7.46(dd,J＝2.0,8.8Hz,1H),7.52(td,J＝1.2,7.2Hz,1H),7.84-7.90(m,2H),8.0(d,J＝8.0Hz,1H),8.04(d,J＝1.6Hz,1H),8.07-8.10(m,2H),8.11-8.14(m,1H),8.16(dd,J＝1.6,8.4Hz,1H),8.25(d,J＝1.6Hz,1H),8.32-8.33(m,1H),8.35(d,J＝8.0Hz,1H),8.45(d,J＝8.4Hz,1H),8.6(m,1H),8.7(m,1H),11.20(s,1H)。
Synthesis of Pt 1: to a 50mL three-necked flask equipped with a magnetic rotor and a condenser tube, intermediate L1 (100mg, 0.167mmol,1.0 equiv.), potassium chloroplatinate (72.8mg, 0.175mmol,1.05 equiv.), n-tetrabutylammonium bromide (5.4mg, 0.0167mmol,0.1 equiv.) were charged, then nitrogen was purged three times, acetic acid (10 mL) was added under nitrogen protection, and bubbling with nitrogen was carried out for 30 minutes. The mixture was stirred at room temperature for 12 hours and then in a 120 ℃ oil bath for 48 hours. Cooling to room temperature, suction filtration of the reaction mixture, washing with water, and recrystallisation of the crude product from dichloromethane/ethyl acetate gave intermediate Pt1 as an orange solid 86mg, 65% yield. 1H NMR (400mhz, cdcl3): δ 1.47 (s, 9H), 1.60 (s, 9H), 7.41-7.45 (m, 3H), 7.65 (d, J =8.0hz, 1h), 7.78 (d, J =8.0hz, 1h), 7.83 (d, J =7.2hz, 1h), 7.88-7.91 (m, 2H), 8.03 (d, J =8.0hz, 1h), 8.05-8.10 (m, 2H), 8.13 (d, J =7.6hz, 1h), 8.20-8.24 (m, 2H), 8.36 (s, 1H), 8.40 (d, J =8.4hz, 1h), 8.45 (d, J =2.0hz, H), 9.24 (d, J = 6.10h).
Example 2: the platinum complex Pt2 can be synthesized by the following route:
Figure BDA0003883681400001011
synthesis of L2: to a 50mL dry three-necked flask with a magnetic rotor was added intermediate 4 (300mg, 0.69mmol,1.0 equiv.), M-2 (291mg, 0.76mmol,1.1 equiv.), K 2 CO 3 (238mg, 1.72mmol,2.5 equiv.), pd (PPh) 3 ) 4 (1695g, 0.0138mmol,0.02 eq), then the nitrogen is pumped three times, and 1,4-dioxane: H is added under the protection of nitrogen 2 O (8ml. The mixture was stirred in an oil bath at 90 ℃ for 24 hours and monitored by thin layer chromatography for starting material AAfter completion of the reaction, part B was unreacted. After cooling to room temperature, the reaction mixture was quenched with water, extracted three times with ethyl acetate and water, and the organic phases were combined and dried over anhydrous sodium sulfate. And (3) distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by using a silica gel chromatographic column, and eluting the eluent: petroleum ether/ethyl acetate =50, and raw material B was recovered back to 100mg to finally obtain intermediate L2 as a white solid at 112mg with a yield of 40%.1H NMR (400MHZ, DMSO): δ 1.44 (s, 9H), 1.49 (s, 9H), 2.17 (s, 3H), 7.15-7.17 (m, 2H), 7.38 (td, J =7.6,0.8Hz, 1H), 7.42 (dd, J =8.4,1.6Hz, 1H), 7.5 (td, J =7.2,1.2Hz, 1H), 7.7 (s, 1H), 7.82 (d, J =8.4Hz, 1H), 8.03 (d, J =2.0hz, 1h), 8.01-8.11 (m, 2H), 8.13-8.16 (m, 2H), 8.23 (d, J =2.0hz, 1h), 8.23-8.35 (m, 2H), 8.44 (s, 1H), 8.45 (d, J =2.0hz, 1h), 8.76 (d, J =1.2hz, 1h), 11.18 (s, 1H).
Synthesis of Pt 2: to a 50mL three-necked flask equipped with a magnetic rotor and condenser was added intermediate L2 (100mg, 0.163mmol,1.0 equiv.), potassium chloroplatinate (72mg, 0.171mmol,1.05 equiv.), n-tetrabutylammonium bromide (5.26mg, 0.0163mmol,0.1 equiv.), then nitrogen was purged three times, acetic acid (10 mL) was added under nitrogen, and bubbling with nitrogen was carried out for 30 minutes. The mixture was stirred at room temperature for 12 hours and then in a 120 ℃ oil bath for 48 hours. Cooling to room temperature, suction filtration of the reaction mixture, washing with water, recrystallisation of the crude product from dichloromethane/ethyl acetate gave the product Pt2 as an orange solid in 68mg, 52% yield. 1H NMR (400mhz, cdcl3): δ 1.47 (s, 9H), 1.60 (s, 9H), 2.38 (s, 3H), 5.35 (t, J =9.0hz, 2h), 6.48-6.50 (m, 1H), 7.54-7.56 (m, 2H), 7.6790 (d, J =8.0hz, 1h), 7.78 (d, J =8.2hz, 1h), 7.83 (d, J =7.64hz, 1h), 8.01-8.06 (m, 2H), 8.08 (d, J =8.8hz, 1h), 8.13 (d, J =7.5hz, 1h), 8.23 (d, J =2.12hz, H), 8.34-8.37 (m, 1H), 8.38-8.41 (m, 38, 1H), 8.16h (J = 6H, 1h), 8.04 (d, 1h).
Example 3: the platinum complex Pt3 can be synthesized by the following route:
Figure BDA0003883681400001021
synthesis of L3: to a 50mL three-necked flask with a magnetic rotor was added intermediate 4 (300mg, 0.69mmol,1.0 equiv),m-3 (226mg, 0.76mmol,1.1 equiv.), K 2 CO 3 (238mg, 1.72mmol,2.5 equiv.), pd (PPh) 3 ) 4 (1695g, 0.0138mmol,0.02 eq), then the nitrogen is pumped three times, and 1,4-dioxane H is added under the protection of nitrogen 2 O (10ml. The mixture was stirred in a 90 ℃ oil bath for 10 hours and thin layer chromatography monitored for completion of the reaction of starting material A and unreacted portion B. After cooling to room temperature, the reaction mixture was quenched with water, extracted three times with ethyl acetate and water, and the organic phases were combined and dried over anhydrous sodium sulfate. And (3) distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by using a silica gel chromatographic column, and eluting the eluent: petroleum ether/ethyl acetate =50, and 90mg of raw material B was recovered back to finally obtain intermediate L3, 105mg of white solid, yield 30%.1H NMR (400MHz, DMSO): δ 1.46 (s, 9H), 1.53 (s, 9H), 7.02 (m, 1H), 7.04 (d, J =0.8Hz, 1H), 7.29-7.31 (m, 2H), 7.45 (dd, J =2.0,8.4Hz, 1H), 7.60-7.65 (m, 2H), 7.73 (ddd, J =2.0,7.2,8.3Hz, 1H), 7.88-7.89 (m, 1H), 7.91 (d, J =8.0Hz, 1H), 7.95 (dt, J =1.6,9.5Hz, 1H), 8.01 (d, J =7.2Hz, 1H), 8.04 (d, J =1.6Hz, 1H), 8.12 (d, 1H = 2.1H), 8.8.24.24 (8.8, 24H, 11H, 11.24H), 11.8.8.8.8.8.8.8.8.8.8 (d, 1H, 11H).
Synthesis of Pt 3: to a 50mL three-necked flask equipped with a magnetic rotor and a condenser, intermediate L3 (100mg, 0.190mmol,1.0 equiv.), potassium chloroplatinate (83mg, 0.2mmol,1.05 equiv.), n-tetrabutylammonium bromide (6.13mg, 0.019mmol,0.1 equiv.) were added, followed by purging nitrogen three times, adding acetic acid (10 mL) under nitrogen, and bubbling with nitrogen for 30 minutes. The mixture was stirred at room temperature for 12 hours and then in a 120 ℃ oil bath for 48 hours. Cooling to room temperature, suction filtration of the reaction mixture, washing with water, and recrystallisation of the crude product from dichloromethane/ethyl acetate gave the product Pt3 as a 62mg solid in 46% yield. 1H NMR (400MHz, CDCl3): delta 1.45 (s, 9H), 1.59 (s, 9H), 7.15-7.20 (m, 2H), 7.58-7.65 (m, 2H), 7.83 (d, J =7.6Hz, 1H), 7.85-7.92 (m, 2H), 8.02-8.10 (m, 2H), 8.2 (d, J =2.0Hz, 1H), 8.32 (s, 1H), 8.38-8.49 (m, 3H), 8.73-8.77 (m, 1H).
Photophysical test and theoretical calculation description
Steady state emission experiments and lifetime measurements were performed on a Horiba Jobin Yvon fluolog-3 spectrometer.The Pt (II) complex was calculated theoretically using the Titan software package. Optimization of ground state (S) using Density Functional Theory (DFT) 0 ) The geometry of the molecule. DFT calculations were performed using the B3LYP functional, with C, H, O and the N atom using the 6-31G (d) base group and the Pt atom using the LANL2DZ base group.
Figure BDA0003883681400001031
As can be seen from fig. 1 to 3, the platinum (II) complex can strongly emit light in a dichloromethane solution, and the solution quantum efficiency is greater than 50%.
Table 1: front line orbital energy level of partial metal complex
Figure BDA0003883681400001032
Figure BDA0003883681400001041
Figure BDA0003883681400001042
The theoretical calculation data for a portion of the platinum (II) complexes are given in Table 1. As can be seen from the table, the front orbital level of the platinum (II) complex can be adjusted by regulating the ligand structure.
As can be seen from fig. 4, HOMO of the two parent nuclei are mainly distributed on the central metal atom and tertiary butyl carbazole, while LUMO is mainly distributed on the pyridine carbazole unit. In Pt4, the t-butyl group introduced on one pyridine ring based on Pt1 hardly participates in the distribution of the front-line orbitals, but can increase steric hindrance and improve thermal stability of the molecule.
As can be seen from fig. 5, in Pt16, a methyl group is introduced at the para position of the nitrogen atom on both pyridine rings based on Pt1, but hardly contributes to the front orbital. According to comparison of Pt65, pt67, pt68 and Pt3, methyl, tert-butyl and phenyl are respectively introduced to pyridine carbazole on Pt3, and the introduced phenyl is found to enable the LUMO distribution to be obviously delocalized towards the upper left; and the energy level differences of Pt65, pt67, pt68 are gradually reduced compared to Pt3, so that it is expected that the emission spectrum thereof will be red-shifted.
As can be seen from fig. 6, the pyridine carbazoles of Pt529 and Pt531 are azapyridine carbazoles, which have little influence on the distribution of the front line molecular orbitals, but have a reduced energy level difference compared to Pt 1. The Pt531 and Pt532 also introduce nitrogen atoms on a benzene ring, and also have no influence on the distribution of a front line orbit, but the energy level difference of the Pt532 is obviously reduced, and the emission spectrum of the Pt532 is expected to generate red shift
The host material involved in the present invention is obtained by a known synthesis method.
Preparing an OLED device: a P-doped material P-1 to P-5 is vapor-deposited on the surface or anode of an ITO glass having a light emitting area of 2mm x 2mm or the P-doped material is co-vapor-deposited with a compound shown in the table at a concentration of 1% to 50% to form a Hole Injection Layer (HIL) of 5 to 100nm and a Hole Transport Layer (HTL) of 5 to 200nm, and then a light emitting layer (EML) (which may contain the compound) of 10to 100nm is formed on the hole transport layer, and finally an Electron Transport Layer (ETL) of 20 to 200nm and a cathode of 50 to 200nm are sequentially formed using the compound, and if necessary, an Electron Blocking Layer (EBL) is added between the HTL and the EML, and an Electron Injection Layer (EIL) is added between the ETL and the cathode, thereby manufacturing an organic light emitting device. The OLEDs were tested by standard methods and are listed in table 3.
Figure BDA0003883681400001051
TABLE 3
Figure BDA0003883681400001052
As can be seen from table 3, compared with comparative device 1 using conventional CBP host material, device examples 1 to 3 using the compound combinations provided by the present invention as hosts can significantly improve the current efficiency of OLED devices while reducing the driving voltage.
In summary, the introduction of functional substituents on biphenyl groups can improve molecular structure and provide less marketing to the front-line orbital distribution of the molecule. Particularly, the tert-butyl group is introduced to the biphenyl group, so that intermolecular pi-pi accumulation can be well inhibited. Similarly, introducing a conjugated group such as acene or benzofuran into a biphenyl group can delocalize HOMO and regulate HOMO energy level. The energy level difference can be obviously changed by replacing the central metal atom with palladium from platinum, the blue shift of the molecular emission spectrum is expected, and the photophysical properties of the molecular emission spectrum can be adjusted.

Claims (14)

1. A complex having a structural formula as shown in formula (I-1) or formula (I-2):
Figure FDA0003883681390000011
wherein:
m is Pt;
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 、Y 8 、Y 9 、Y 10 、Y 11 、Y 12 、Y 13 、Y 14 、Y 15 、Y 16 、Y 17 、Y 18 、Y 19 and Y 20 Each independently is N or CH;
R 1 、R 2 、R 3 、R 4 、R 5 and R 6 Each independently represents mono-, di-, tri-or no substitution; r 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, a,Alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted or unsubstituted arylamino, substituted or unsubstituted heteroarylamino, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted aryloxysilyl, substituted or unsubstituted heteroaryloxysilyl, substituted or unsubstituted arylacyl, substituted or unsubstituted heteroarylacyl, substituted or unsubstituted phosphinyl, and two or more adjacent R' s 1 、R 2 、R 3 、R 4 、R 5 And R 6 May be selectively linked to form fused rings.
2. A composition is characterized by comprising a tetradentate ring metal platinum (II) complex phosphorescent material based on carbazole-pyridine derivatives and an organic host material, wherein the structural formula of the metal platinum (II) complex phosphorescent material is shown as a formula (I-1) or (I-2); the organic host material has a structural formula (II) or (III):
Figure FDA0003883681390000021
wherein:
in the formulae (I-1) and (I-2), M is Pt; y is 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 、Y 8 、Y 9 、Y 10 、Y 11 、Y 12 、Y 13 、Y 14 、Y 15 、Y 16 、Y 17 、Y 18 、Y 19 And Y 20 Each independently is N or CH; r 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents mono-, di-, tri-or no substitution; r 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents any one of hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxyl group, a hydrazino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, an alkylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroaryloxy group, and two or more adjacent R groups 1 、R 2 、R 3 、R 4 、R 5 And R 6 May be optionally linked to form fused rings;
in the formulae (II) and (III), X 1 、X 2 、X 3 、X 4 、X3 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 、X 12 、X 13 、X 14 、X 15 、X 16 、X 17 、X 18 、X 19 And X 20 Each independently is N or CH; z 1 、Z 2 、Z 3 、Z 4 、Z 5 、Z 6 、Z 7 、Z 8 、Z 9 、Z 10 、Z 11 、Z 12 And Z 13 Each independently is N or CH, and at least 2 are N; l is 1 、L 2 And L 3 Absent or selected from single bonds, O, S, CR 15 R 16 、SiR 17 R 18 、NR 19 (ii) a A. B, C and D are each independently selected from the group consisting of C6-C30 aryl, C2-A C30 heteroaryl group; r is 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R 19 Each independently represents mono-, di-, tri-, tetra-, or unsubstituted; and R is 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R 19 Each independently represents any one of hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxyl group, a hydrazine group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, an alkylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroaryloxy group, and two or more adjacent R 1 、R 2 、R 3 、R 4 、R 5 And R 6 May be selectively linked to form fused rings.
3. The platinum (II) complex according to claim 2, characterized in that the platinum (II) complex has the structure of one of the following:
Figure FDA0003883681390000041
Figure FDA0003883681390000051
Figure FDA0003883681390000061
Figure FDA0003883681390000071
Figure FDA0003883681390000081
Figure FDA0003883681390000091
Figure FDA0003883681390000101
Figure FDA0003883681390000111
Figure FDA0003883681390000121
Figure FDA0003883681390000131
Figure FDA0003883681390000141
Figure FDA0003883681390000151
Figure FDA0003883681390000161
Figure FDA0003883681390000171
Figure FDA0003883681390000181
Figure FDA0003883681390000191
Figure FDA0003883681390000201
Figure FDA0003883681390000211
Figure FDA0003883681390000221
4. the composition according to claim 2, wherein formula (II) is selected from the group consisting of compounds described in (II) -1 to (II) -24:
Figure FDA0003883681390000231
Figure FDA0003883681390000241
wherein, X 1 、X 2 、X 3 、X 4 、X 5 、X 6 、X 7 、X 8 、X 9 And X 10 ，L 1 、L 2 And L 3 A and B, R 7 、R 8 、R 9 And R 10 The same as in claim 1.
5. The composition of claim 2, wherein A, B, C and D are selected from the group of structures:
Figure FDA0003883681390000242
wherein R is 15 、R 16 、R 17 、R 18 And R 19 The same as in claim 1.
6. The composition of claim 2, wherein the organic host material of formula (II) or formula (III) is selected from one of the following representative structures:
Figure FDA0003883681390000251
Figure FDA0003883681390000261
Figure FDA0003883681390000271
Figure FDA0003883681390000281
Figure FDA0003883681390000291
Figure FDA0003883681390000301
Figure FDA0003883681390000311
Figure FDA0003883681390000321
Figure FDA0003883681390000331
Figure FDA0003883681390000341
Figure FDA0003883681390000351
Figure FDA0003883681390000361
Figure FDA0003883681390000371
Figure FDA0003883681390000381
Figure FDA0003883681390000391
Figure FDA0003883681390000401
Figure FDA0003883681390000411
Figure FDA0003883681390000421
Figure FDA0003883681390000431
Figure FDA0003883681390000441
Figure FDA0003883681390000451
Figure FDA0003883681390000461
Figure FDA0003883681390000471
Figure FDA0003883681390000481
Figure FDA0003883681390000491
Figure FDA0003883681390000501
Figure FDA0003883681390000511
Figure FDA0003883681390000521
Figure FDA0003883681390000531
Figure FDA0003883681390000541
Figure FDA0003883681390000551
Figure FDA0003883681390000561
Figure FDA0003883681390000571
Figure FDA0003883681390000581
Figure FDA0003883681390000591
Figure FDA0003883681390000601
Figure FDA0003883681390000611
Figure FDA0003883681390000621
Figure FDA0003883681390000631
Figure FDA0003883681390000641
Figure FDA0003883681390000651
Figure FDA0003883681390000661
Figure FDA0003883681390000671
Figure FDA0003883681390000681
Figure FDA0003883681390000691
Figure FDA0003883681390000701
Figure FDA0003883681390000711
Figure FDA0003883681390000721
Figure FDA0003883681390000731
Figure FDA0003883681390000741
Figure FDA0003883681390000751
Figure FDA0003883681390000761
Figure FDA0003883681390000771
Figure FDA0003883681390000781
Figure FDA0003883681390000791
Figure FDA0003883681390000801
Figure FDA0003883681390000811
Figure FDA0003883681390000821
Figure FDA0003883681390000831
Figure FDA0003883681390000841
7. a formulation comprising a composition according to any one of claims 2 to 6 and at least one solvent.
8. A formulation according to claim 7, wherein the composition and solvent form a formulation in which the solvent is an unsaturated hydrocarbon solvent, a halogenated saturated hydrocarbon solvent, a halogenated unsaturated hydrocarbon solvent, an ether solvent or an ester solvent; wherein the unsaturated hydrocarbon solvent is toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene or tert-butylbenzene; the halogenated saturated hydrocarbon solvent is carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane or bromocyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; the ester solvent is alkyl benzoate.
9. An organic electroluminescent device, comprising: a first electrode; a second electrode facing the first electrode; the organic functional layer is clamped between the first electrode and the second electrode; wherein the light-emitting layer comprises the composition of any one of claims 2 to 6.
10. The organic electroluminescent device according to claim 8, wherein the luminescent layer contains the carbazole derivative-based tetradentate cyclometalated platinum (II) complex phosphorescent material and an organic host material, and wherein the carbazole derivative tetradentate cyclometalated platinum (II) complex phosphorescent material is present in an amount of 1 to 50% by mass.
11. The organic electroluminescent device according to claim 9, wherein the device is a full-color display, a photovoltaic device, a light-emitting display device, or an organic light-emitting diode.
12. An organic electroluminescent device comprising a cathode layer, an anode layer and an organic layer, the organic layer comprising a composition comprising a tetracyclic cyclometalated platinum (II) complex phosphorescent material based on a carbazole-pyridine derivative and an organic host material, wherein the structural formula of the metal platinum (II) complex phosphorescent material is shown as formulas (I-1) and (I-2); the organic host material has a structural formula (II) or (III):
Figure FDA0003883681390000851
wherein:
in the formulae (I-1) and (I-2), M is Pt; y is 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 、Y 8 、Y 9 、Y 10 、Y 11 、Y 12 、Y 13 、Y 14 、Y 15 、Y 16 、Y 17 、Y 18 、Y 19 And Y 20 Each independently is N or CH; r 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents mono-, di-, tri-or no substitution; r is 1 、R 2 、R 3 、R 4 、R 5 And R 6 Each independently represents any one of hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxyl group, a hydrazino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, an alkylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroaryloxy group, and two or more adjacent R groups 1 、R 2 、R 3 、R 4 、R 5 And R 6 May be optionally linked to form fused rings;
in the formulae (II) and (III), X 1 、X 2 、X 3 、X 4 、X3 5 、X 6 、X 7 、X 8 、X 9 、X 10 、X 11 、X 12 、X 13 、X 14 、X 15 、X 16 、X 17 、X 18 、X 19 And X 20 Each independently is N or CH; z 1 、Z 2 、Z 3 、Z 4 、Z 5 、Z 6 、Z 7 、Z 8 、Z 9 、Z 10 、Z 11 、Z 12 And Z 13 Each independently is N or CH, and at least 2 are N; l is 1 、L 2 And L 3 Absent or selected from a single bond, O, S, CR 15 R 16 、SiR 17 R 18 、NR 19 (ii) a A. B, C and D are each independently selected from the group consisting of C6-C30 aryl, C2-C30 heteroaryl; r 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R 19 Each independently represents mono-, di-, tri-, tetra-, or unsubstituted; and R is 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R 19 Each independently represents hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a,A phosphoramide group, an imine group, a sulfo group, a carboxyl group, a hydrazine group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, an alkylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted aryloxysilyl group, a substituted or unsubstituted heteroaryloxysilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroarylacyl group, a substituted or unsubstituted phosphinyl group, and two or more adjacent R groups 1 、R 2 、R 3 、R 4 、R 5 And R 6 May be selectively linked to form fused rings.
13. A display or lighting device comprising the organic electroluminescent element as claimed in any one of claims 9 to 11.
14. Use of a composition according to claim 2 for the manufacture of an organic electroluminescent device.
CN202211242176.9A 2022-10-11 2022-10-11 Composition, preparation, organic electroluminescent device and display or lighting device Pending CN115557999A (en)

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US20180090707A1 (en) * 2016-09-27 2018-03-29 Samsung Electronics Co., Ltd. Organometallic compound, organic light-emitting device including the organometallic compound, and diagnosis composition including the organometallic compound
US20180362567A1 (en) * 2017-06-16 2018-12-20 Samsung Electronics Co., Ltd. Organometallic compound, organic light-emitting device including the organometallic compound, and diagnostic composition including the organometallic compound
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US20180090707A1 (en) * 2016-09-27 2018-03-29 Samsung Electronics Co., Ltd. Organometallic compound, organic light-emitting device including the organometallic compound, and diagnosis composition including the organometallic compound
US20180362567A1 (en) * 2017-06-16 2018-12-20 Samsung Electronics Co., Ltd. Organometallic compound, organic light-emitting device including the organometallic compound, and diagnostic composition including the organometallic compound
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