CN112652731B - Composition and organic electroluminescent element comprising same - Google Patents

Composition and organic electroluminescent element comprising same Download PDF

Info

Publication number
CN112652731B
CN112652731B CN202011571801.5A CN202011571801A CN112652731B CN 112652731 B CN112652731 B CN 112652731B CN 202011571801 A CN202011571801 A CN 202011571801A CN 112652731 B CN112652731 B CN 112652731B
Authority
CN
China
Prior art keywords
formula
substituted
unsubstituted
composition
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011571801.5A
Other languages
Chinese (zh)
Other versions
CN112652731A (en
Inventor
王子兴
夏蓉蓉
陈清泉
吴空物
赵晓宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Huadisplay Optoelectronics Co Ltd
University of Shanghai for Science and Technology
Original Assignee
Zhejiang Huadisplay Optoelectronics Co Ltd
University of Shanghai for Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Huadisplay Optoelectronics Co Ltd, University of Shanghai for Science and Technology filed Critical Zhejiang Huadisplay Optoelectronics Co Ltd
Priority to CN202011571801.5A priority Critical patent/CN112652731B/en
Publication of CN112652731A publication Critical patent/CN112652731A/en
Application granted granted Critical
Publication of CN112652731B publication Critical patent/CN112652731B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Abstract

The invention belongs to the field of organic photoelectricity, and particularly relates to a composition containing an iridium metal complex and an organic compound and an organic electroluminescent element containing the composition, in particular to an organic electroluminescent diode, wherein the iridium metal complex has a structure shown in a formula (I), and the organic compound has a structure formula (II) or (III):
Figure DDA0002862937880000011
the iridium metal complex formula (I), the organic compound formula (II) or formula (III), and the organic photoelectric element can be understood by referring to the specific description provided herein. The composition is applied to a light-emitting layer of an organic light-emitting diode, so that the current efficiency of a light-emitting element is improved, the driving voltage is obviously reduced, the service life is prolonged, and the composition has good commercialization prospect.

Description

Composition and organic electroluminescent element comprising same
Technical Field
The invention belongs to the field of organic electroluminescence, and particularly relates to a composition of an iridium metal complex and an organic compound, and an organic electroluminescent element containing the composition.
Background
As a novel display technology, the organic electroluminescent element has the unique advantages of self luminescence, wide viewing angle, low energy consumption, high efficiency, thinness, rich colors, high response speed, wide application temperature range, low driving voltage, capability of manufacturing flexible, bendable and transparent display panels, environmental friendliness and the like, can be applied to flat panel displays and new generation illumination, and can also be used as a backlight source of an LCD.
Since the invention in the 20 th century and the 80 s, organic electroluminescent devices have been used in industry, such as display screens of mobile phones, but the current OLED devices have been restricted to wider applications, especially large-screen displays, due to low efficiency, short service life and other factors. And the most important factor restricting the wide application thereof is the performance of the organic electroluminescent material. Meanwhile, when an OLED device is operated by applying a voltage, joule heat is generated, so that organic materials are easily crystallized, and the lifetime and efficiency of the device are affected.
Since the ratio of the singlet excited state to the triplet excited state due to charge binding is theoretically estimated to be 1:3, the use of a small molecular fluorescent material is considered to be only 25% of the total energy available for light emission, and the remaining 75% of the energy is lost due to the non-light-emitting mechanism of the triplet excited state, so that the internal quantum efficiency limit of the fluorescent material is considered to be 25%. Professor Baldo and Forrest in 1998 found that triplet phosphorescence can be utilized at room temperature, and the upper limit of the original internal quantum efficiency is increased to 100%, and triplet phosphors are often heavy metal atoms and are formed of complexes, and by utilizing the heavy atom effect, the strong spin-orbit coupling effect causes the energy levels of the singlet excited state and the triplet excited state to be mixed with each other, so that the originally forbidden triplet energy is relieved to emit light in the form of phosphorescence, and the quantum efficiency is greatly increased.
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. Commonly used phosphorescent organic host materials such as CBP (4, 4' -bis (9-carbazolyl) -biphenyl) have high efficiency and high triplet energy levels, which, when used as an organic material, can be efficiently transferred from a light-emitting organic material to a guest phosphorescent light-emitting material. A commonly used organic guest material is an iridium metal complex.
The invention discovers that the combination of a specific organic compound and an iridium metal compound can be used as a light-emitting layer of an organic electroluminescent element to remarkably improve the current efficiency of the organic electroluminescent element, reduce the operating voltage of the element and prolong the service life of the element.
Disclosure of Invention
The invention aims to provide a composition of an iridium metal complex and an organic compound and an organic electroluminescent element comprising the composition.
The invention provides a composition of an iridium metal complex and an organic compound, wherein the iridium metal complex has a structure shown as a formula (I), and the organic compound has a structural formula (II) or (III):
Figure BDA0002862937860000021
in the formula (I), A1 forms five-membered ring selected from C1-C60 alkyl, C1-C60 alkoxy, C1-C60 alkylsilyl, C1-C60 alkoxysilyl, C6-C40 aryl and C1-C40 heteroaryl; x is selected from NR1, O, S, CR1R2, SiR1R2, O ═ P-R1, or B-R1; y is selected from N or C-R2; R1-R3 are independently selected from any one of hydrogen, deuterium, halogen, C1-C18 alkyl, C1-C18 alkoxy, C1-C18 alkylsilyl, C1-C18 alkoxy silyl, C6-C40 aryl, C1-C40 heteroaryl, substituted or unsubstituted arylether group, substituted or unsubstituted heteroarylether group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamine group, substituted or unsubstituted arylsilicon group, substituted or unsubstituted heteroarylsilicon group, substituted or unsubstituted aryloxysilyl group, substituted or unsubstituted arylacyl group, substituted or unsubstituted heteroarylacyl group, and substituted or unsubstituted phosphinyl group; (L ^ Z) is an auxiliary ligand, a bidentate ligand, the same as or different from the main ligand on the left side of the structural formula; m is taken from 1, 2 or 3, and m + n is 3; heteroaryl means containing B, N, O, S, P (═ O), Si, and at least one heteroatom of P.
In formula (II) and formula (III), X1 to X6 are CR or N; Y1-Y8 are CR or N, and at least 2 are N; l is absent or selected from single bond, O, S, CRR, SiRR, NR; a and B are each independently selected from the group consisting of C6-C30 aryl, C2-C30 heteroaryl; r is independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, aryl or heteroaryl substituted amine; n is an integer of 0 to 6; adjacent X or Y may form a ring; all groups may be partially deuterated or fully deuterated.
Preferably wherein (L ^ Z) of the iridium metal complex of formula (I) in the composition is selected from one of the following representative structural formulae:
Figure BDA0002862937860000031
wherein Y is selected from O or N; R1-R3 are independently selected from C1-C18 alkyl, C1-C18 alkoxy, alkyl silicon group containing C1-C18, alkoxy silicon group containing C1-C18, aryl group containing C6-C40 and heteroaryl group containing C1-C40; a and B are selected from C1-C60 alkyl, C1-C60 alkoxy, C1-C60 alkylsilyl, C1-C60 alkoxysilyl, C6-C40 aryl, C1-C40 heteroaryl, A2 and B2 can be mono-substituted or poly-substituted according to valence principles, and all the groups can be partially deuterated or fully deuterated.
Preferably, the composition of the present invention, wherein the iridium metal complex of formula (I) has a structure selected from the following representative structures:
Figure BDA0002862937860000032
Figure BDA0002862937860000041
preferably, the composition of the present invention, wherein (L ^ Z) in the iridium metal complex of formula (I) is one selected from the following representative structural formulae:
Figure BDA0002862937860000042
wherein X is selected from NR1, O, S, CR1R2, SiR1R2, O ═ P-R1, or B-R1; R1-R3 are independently selected from C1-C18 alkyl, C1-C18 alkoxy, alkyl silicon group containing C1-C18, alkoxy silicon group containing C1-C18, aryl group containing C6-C40 and heteroaryl group containing C1-C40, and can be partially deuterated or fully deuterated.
Preferably, the iridium metal complex of the present invention is selected from one of the following structures, but does not represent a limitation thereto:
Figure BDA0002862937860000051
Figure BDA0002862937860000061
Figure BDA0002862937860000071
Figure BDA0002862937860000081
Figure BDA0002862937860000091
Figure BDA0002862937860000101
Figure BDA0002862937860000111
Figure BDA0002862937860000121
Figure BDA0002862937860000131
Figure BDA0002862937860000141
Figure BDA0002862937860000151
Figure BDA0002862937860000161
Figure BDA0002862937860000171
Figure BDA0002862937860000181
Figure BDA0002862937860000191
Figure BDA0002862937860000201
Figure BDA0002862937860000211
Figure BDA0002862937860000221
Figure BDA0002862937860000231
Figure BDA0002862937860000241
the present invention provides compositions wherein the organic compound is preferably selected from the compounds described in formula II-1 to II-7 when the structure is of formula (II),
but are not meant to be limited thereto:
Figure BDA0002862937860000251
wherein X1 to X6, L, A, B, R, n are the same as described above.
Preferably, a and B are selected from the group described by the following structures, but do not represent a limitation thereto:
Figure BDA0002862937860000252
wherein X1 to X6, Y1 to Y8, L, R, n are the same as described above.
Preferably, one organic compound represented by formula (II) or formula (III) is selected from at least one of the following representative structures, but not represented by way of limitation:
Figure BDA0002862937860000261
Figure BDA0002862937860000271
Figure BDA0002862937860000281
Figure BDA0002862937860000291
Figure BDA0002862937860000301
Figure BDA0002862937860000311
Figure BDA0002862937860000321
Figure BDA0002862937860000331
Figure BDA0002862937860000341
Figure BDA0002862937860000351
Figure BDA0002862937860000361
Figure BDA0002862937860000371
Figure BDA0002862937860000381
Figure BDA0002862937860000391
Figure BDA0002862937860000401
Figure BDA0002862937860000411
Figure BDA0002862937860000421
Figure BDA0002862937860000431
Figure BDA0002862937860000441
Figure BDA0002862937860000451
Figure BDA0002862937860000461
Figure BDA0002862937860000471
Figure BDA0002862937860000481
Figure BDA0002862937860000491
Figure BDA0002862937860000501
Figure BDA0002862937860000511
Figure BDA0002862937860000521
Figure BDA0002862937860000531
Figure BDA0002862937860000541
Figure BDA0002862937860000551
Figure BDA0002862937860000561
Figure BDA0002862937860000571
Figure BDA0002862937860000581
Figure BDA0002862937860000591
Figure BDA0002862937860000601
Figure BDA0002862937860000611
Figure BDA0002862937860000621
Figure BDA0002862937860000631
Figure BDA0002862937860000641
Figure BDA0002862937860000651
Figure BDA0002862937860000661
Figure BDA0002862937860000671
Figure BDA0002862937860000681
Figure BDA0002862937860000691
Figure BDA0002862937860000701
Figure BDA0002862937860000711
Figure BDA0002862937860000721
Figure BDA0002862937860000731
Figure BDA0002862937860000741
Figure BDA0002862937860000751
Figure BDA0002862937860000761
Figure BDA0002862937860000771
Figure BDA0002862937860000781
Figure BDA0002862937860000791
Figure BDA0002862937860000801
Figure BDA0002862937860000811
Figure BDA0002862937860000821
Figure BDA0002862937860000831
the solvent used in the present invention is not particularly limited, and examples thereof include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decahydronaphthalene, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, etc., halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, etc., ether solvents such as tetrahydrofuran, tetrahydropyran, etc., ester solvents such as alkyl benzoate, etc., which are well known to those skilled in the art.
The present invention also relates to an organic opto-electronic 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.
The mass percentage of the iridium metal complex in the formula (I) in the light-emitting layer of the organic electroluminescent device is 0.1-50%.
In the present invention, the organic electroluminescent element is an anode which can be formed by depositing metal, an oxide having conductivity, or an alloy thereof on a substrate by a sputtering method, electron beam evaporation, vacuum deposition, or the like; and sequentially evaporating a hole injection layer, a hole transport layer, a luminescent layer, a hole blocking layer and an electron transport layer on the surface of the prepared anode, and then evaporating a cathode. The organic electroluminescent device is manufactured by sequentially evaporating the cathode, the organic layer and the anode on the external substrate by the 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 device layers can be reduced.
The materials used for the organic electroluminescent element according to the present invention may be classified into top emission, bottom emission, or double-sided emission. The compounds of the organic electroluminescent device according to the embodiment of the present invention can be applied to the aspects of organic light emitting cells, illuminating OLEDs, flexible OLEDs, organic photoreceptors, organic thin film transistors and other optoelectronic elements in a similar principle to the organic light emitting device.
The invention has the beneficial effects that:
the invention relates to a novel iridium metal complex and an organic compound composition, which have better thermal stability, the organic compound can balance the transport of holes and electrons, and the energy transmission between the organic compound and the iridium metal complex in the composition is more efficient.
Drawings
FIG. 1 is a structural diagram of an organic electroluminescent diode device according to the present invention.
Where 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
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In a preferred embodiment of the present invention, in which the OLED device according to the invention comprises a hole transport layer, the hole transport material may preferably be selected from known or unknown materials, particularly preferably from, but not limiting the invention to, the following structures:
Figure BDA0002862937860000851
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 BDA0002862937860000852
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 structure:
Figure BDA0002862937860000861
the organic compounds referred to in the present invention are obtained by known synthetic methods.
The general synthesis steps of the iridium metal complex related to the formula (I) are as follows:
Figure BDA0002862937860000862
the general procedure is as follows,
(1) under the protection of argon, ligand 1 or L ^ Z (0.10 mol) and IrCl3.3H2Heating and refluxing a mixed solution of O (0.045 mol), 2-ethoxyethanol (300 ml) and water (100 ml) for 16-20 hours until a supernatant is taken, detecting the content of the ligand 1 to be less than 5% by using high performance liquid chromatography, stopping heating, cooling to room temperature, performing suction filtration by using a Buchner funnel, leaching a filter cake by using a mixed solution of water and 2-ethoxyethanol, and drying to obtain a yellow powder bridged dimer 2 or 3, wherein the yield is 81-89%.
(2) Adding dichloro crosslinked dimer complex (2.2mmol), ligand L ^ Z or ligand 1(2.4mmol), anhydrous sodium carbonate (1.2g,10.8mmol) and 80ml of 2-ethoxyethanol into a double-neck round-bottom flask, heating and refluxing for 6 hours, stopping heating, cooling to room temperature, adding a proper amount of distilled water, and filtering to obtain a solid. The solid was dissolved in dichloromethane and passed through a short column of silica gel. Removing the solvent under reduced pressure, and washing the solid obtained by concentration with methanol and petroleum ether in sequence to obtain the final target product.
Ligand 1 was obtained by custom synthesis. These are merely examples illustrating embodiments of the present invention and the scope of the present invention is not limited thereto.
Example 1: synthesis of Compound 1
Figure BDA0002862937860000871
Referring to the general synthetic route, L ^ Z represents n-pentane-2, 4-dione, and the yield of the final product is 74%. Mass spectrum m/z, theoretical 1160.7; found M + H: 1161.6.
example 2: synthesis of Compound 2
Figure BDA0002862937860000872
Referring to the general synthetic route, L ^ Z represents n-heptane-3, 5-dione, with a yield of 72% of the final product. Mass spectrum m/z, theoretical 1086.5; found M + H: 1087.5.
example 3: synthesis of Compound 3
Figure BDA0002862937860000881
Referring to the general synthetic route, L ^ Z represents 2, 6-dimethylheptane-3, 5-dione, with a yield of 75% of the final product. Mass spectrum m/z, theoretical 1160.7; found M + H: 1161.7.
example 4: synthesis of Compound 4
Figure BDA0002862937860000882
Referring to the general synthetic route, L ^ Z represents 2, 2, 6, 6-tetramethylheptane-3, 5-dione, and the yield of the final product is 79%. Mass spectrum m/z, theoretical 1136.6; found M + H: 1137.6.
example 5: synthesis of Compound 5
Figure BDA0002862937860000883
Referring to the general synthetic route, L ^ Z represents 3, 7-diethyl, 3, 7-dimethylnonane 4, 6-dione, with a yield of 73% of final product. Mass spectrum m/z, theoretical 1192.7; found M + H: 1193.7.
example 6: synthesis of Compound 6
Figure BDA0002862937860000891
Referring to the general synthetic route, L ^ Z represents n-pentane-2, 4-dione, and the yield of the final product is 71%. Mass spectrum m/z, theoretical 1220.7; found M + H: 1221.7.
example 7: synthesis of Compound 7
Figure BDA0002862937860000892
Referring to the general synthetic route, L ^ Z represents n-heptane-3, 5-dione, and the yield of the final product is 76%. Mass spectrum m/z, theoretical 1316.6; found M + H: 1317.6.
example 8: synthesis of Compound 8
Figure BDA0002862937860000893
Referring to the general synthetic route, L ^ Z represents n-pentane 2, 4 dione, and the yield of the final product is 81%. Mass spectrum m/z, theoretical 1217.43; found M + H: 1218.4.
example 9: synthesis of Compound 9
Figure BDA0002862937860000901
Referring to the general synthetic route, L ^ Z represents n-heptane-3, 5-dione, and the yield of the final product is 82%. Mass spectrum m/z, theoretical 1162.7; found M + H: 1163.7.
example 10: synthesis of Compound 10
Figure BDA0002862937860000902
Referring to the general synthetic route, L ^ Z represents 2, 6-dimethylheptane-3, 5-dione, with a yield of 83% of the final product. Mass spectrum m/z, theoretical 1119.6; found M + H: 1120.6.
example 11: synthesis of Compound 11
Figure BDA0002862937860000903
Referring to the general synthetic route, L ^ Z represents 3, 7-diethylnonane-4, 6-dione with a yield of 71% of the final product. Mass spectrum m/z, theoretical 1218.7; found M + H: 1219.7.
example 12: synthesis of Compound 12
Figure BDA0002862937860000911
Referring to the general synthetic route, L ^ Z represents n-pentane-2, 4-dione, and the yield of the final product is 69%. Mass spectrum m/z, theoretical 1054.5; found M + H: 1055.5.
example 13: synthesis of Compound 13
Figure BDA0002862937860000912
Referring to the general synthetic route, L ^ Z represents 2, 6-dimethylheptane-3, 5-dione, with a yield of 76% of the final product. Mass spectrum m/z, theoretical 1186.5; found M + H: 1187.5.
example 14: synthesis of Compound 14
Figure BDA0002862937860000913
Referring to the general synthetic route, L ^ Z represents 3, 7-diethylnonane-4, 6-dione, and the yield of the final product is 74%. Mass spectrum m/z, theoretical 1274.8; found M + H: 1275.8.
example 15: synthesis of Compound 15
Figure BDA0002862937860000914
Referring to the general synthetic route, ligand stands for 3, 7-diethyl, 3, 7-dimethylnonane 4, 6-dione, with a yield of 72% of the final product. Mass spectrum m/z, theoretical 1127.5; found M + H: 1128.5.
example 16: synthesis of Compound 16
Figure BDA0002862937860000921
Referring to the general synthetic route, L ^ Z represents n-pentane-2, 4-dione, and the yield of the final product is 71%. Mass Spectrometry M/z, theoretical 1108.6 found M + H: 1109.7.
example 17: synthesis of Compound 17
Figure BDA0002862937860000922
Referring to the general synthetic route, L ^ Z represents n-heptane-3, 5-dione, with a yield of 76% of the final product. Mass spectrum m/z, theoretical 1054.5; found M + H: 1055.5.
example 18: synthesis of Compound 18
Figure BDA0002862937860000923
Referring to the general synthetic route, L ^ Z represents 2, 6-dimethylheptane-3, 5-dione, and the yield of the final product is 77%. Mass spectrum m/z, theoretical value 1064.4; found M + H: 1065.4.
example 19: synthesis of Compound 19
Figure BDA0002862937860000931
Referring to the general synthetic route, L ^ Z represents 3, 7-diethylnonane-4, 6-dione, with a yield of 79% of the final product. Mass spectrum m/z, theoretical 1204.5; found M + H: 1205.5.
example 20: synthesis of Compound 20
Figure BDA0002862937860000932
Referring to the general synthetic route, L ^ Z represents n-heptane-3, 5-dione, and the yield of the final product is 74%. Mass spectrum m/z, theoretical 1200.5; found M + H: 1201.5.
example 21: synthesis of Compound 21
Figure BDA0002862937860000933
Referring to the general synthetic route, L ^ Z represents 2, 6-dimethylheptane-3, 5-dione, with a yield of 81% of the final product. Mass spectrum m/z, theoretical 1108.6; found M + H: 1109.6.
example 22: synthesis of Compound 22
Figure BDA0002862937860000941
Referring to the general synthetic route, L ^ Z represents 3, 7-diethylnonane-4, 6-dione, with a yield of 80% of the final product. Mass spectrum m/z, theoretical 1252.61; found M + H: 1253.6.
example 23: synthesis of Compound 23
Figure BDA0002862937860000942
Referring to the general synthetic route, L ^ Z represents 3, 7-diethyl, 3, 7-dimethylnonane 4, 6-dione, with a yield of 81% of final product. Mass spectrum m/z, theoretical 1198.6; found M + H: 1199.6.
example 24: synthesis of Compound 24
Figure BDA0002862937860000943
Referring to the general synthetic route, L ^ Z represents n-heptane-3, 5-dione, and the yield of the final product is 78%. Mass spectrum m/z, theoretical 1060.4; found M + H: 1061.4.
example 25: synthesis of Compound 25
Figure BDA0002862937860000944
Referring to the general synthetic route, L ^ Z represents n-pentane-2, 4-dione, and the yield of the final product is 80%. Mass spectrum m/z, theoretical 1004.35; found M + H: 1005.3.
example 26: synthesis of Compound 26
Figure BDA0002862937860000951
Referring to the general synthetic route, L ^ Z represents 3, 7-diethylnonane-4, 6-dione, and the yield of the final product is 83%. Mass spectrum m/z, theoretical 1150.45; found M + H: 1151.4.
example 27: synthesis of Compound 27
Figure BDA0002862937860000952
Referring to the general synthetic route, the yield of the final product was 73%. Mass spectrum m/z, theoretical 992.49; found M + H: 993.5.
manufacturing of OLED device:
a P-doped material P-1 to P-5 is evaporated on the surface or anode of ITO/Ag/ITO glass with the size of 2mm multiplied by 2mm in light emitting area or the P-doped material is co-evaporated with the compound in the table with the concentration of 1% to 50% to form a Hole Injection Layer (HIL) with the thickness of 5 nm to 100nm and a Hole Transport Layer (HTL) with the thickness of 5 nm to 200nm, then a light emitting layer (EML) (which can contain the compound) with the thickness of 10 nm to 100nm is formed on the hole transport layer, finally an Electron Transport Layer (ETL) with the thickness of 20 nm to 200nm and a cathode with the thickness of 50 nm to 200nm are formed by the compound in sequence, if necessary, an Electron Blocking Layer (EBL) is added between the HTL and the EML layer, and an Electron Injection Layer (EIL) is added between the ETL and the cathode, thereby manufacturing the organic light emitting element. The OLEDs were tested by standard methods, as listed in table 1.
To better illustrate the practical gain effect of the present invention, comparative organic electroluminescent devices were prepared using the following commonly used iridium metal complex RD-1 and iridium metal complexes of the present invention and organic compounds H-1 to H-14 as the main components to illustrate the superiority of the composition of the present invention.
Figure BDA0002862937860000961
In the specific embodiment, the top-emitting OLED device is formed on ITO/Ag/ITO-containing glass, HIL is HT-1: P-3(97:3 v/v%), and the thickness is 10 nanometers; HTL is HT-1, and the thickness is 100 nanometers; EBL is HT-8, thickness is 10 nm, EML is the composition of the invention, concretely, (H-1-H-14): (RD-1-RD-6) (97:3 v/v%), thickness is 35 nm, ETL is ET-13: LiQ (50:50 v/v%) with a thickness of 35 nm, then evaporating a cathode Yb of 1 nm, an Ag of 14 nm and an evaporated CPL layer of 70 nm. The characteristics of efficiency, operating voltage, life, etc. according to the above examples and comparative examples are shown in table 1 below.
TABLE 1
Figure BDA0002862937860000962
Figure BDA0002862937860000971
As can be seen from Table 1, fused rings are incorporated on the ligand structure, and the current efficiency of the OLED device can be obviously improved and the driving voltage can be reduced by using the composition provided by the invention under the same conditions from the device 1 to the device example 23 and the comparison devices 1 to 5. Specifically, comparing the device 1 with the device examples 1-11, the combination provided by the invention has obvious advantages. If a new combination is adopted, namely the device examples 12 to 23 have lower operating voltage, higher luminous efficiency and longer service life obviously compared with the comparative devices 3 to 5. The composition provided by the invention has obvious superiority and commercial application value.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (12)

1. The composition is characterized by comprising an iridium metal complex and an organic compound, wherein the structural formula of the iridium metal complex is shown as a formula (I); the structural formula of the organic compound is shown as the formula (II) or the formula (III)
Figure FDA0003668602610000011
In the formula (I), A1 forms a five-membered ring selected from C1-C60 alkyl, C1-C60 alkoxy, C1-C60 alkylsilyl, C1-C60 alkoxy silicon, C6-C40 aryl, or C1-C40 heteroaryl; x is selected from NR1, O, S, CR1R2, SiR1R2, O ═ P-R1, or B-R1; y is selected from N or C-R2; R1-R3 are independently selected from any one of hydrogen, deuterium, halogen, C1-C18 alkyl, C1-C18 alkoxy, C1-C18 alkylsilyl, C1-C18 alkoxysilyl, C6-C40 aryl, C1-C40 heteroaryl, substituted or unsubstituted arylether group, substituted or unsubstituted heteroarylether group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamine group, substituted or unsubstituted arylsilicon group, substituted or unsubstituted heteroarylsilicon group, substituted or unsubstituted aryloxysilyl group, substituted or unsubstituted arylacyl group, substituted or unsubstituted heteroarylacyl group, and substituted or unsubstituted phosphinyl group; (L ^ Z) is an auxiliary ligand, is a bidentate ligand and is the same as or different from the main ligand on the left side of the structural formula; m is taken from 1, 2 or 3, and m + n is 3; heteroaryl means containing B, N, O, S, P (═ O), Si, P at least one heteroatom;
in formula (II) and formula (III), X1 to X6 are CR or N; y1 to Y8 are CR or N, and at least 2 are N; l is absent or selected from a single bond, O, S, CRR, SiRR, or NR; a and B are each independently selected from C6-C30 aryl, or C2-C30 heteroaryl; r is independently selected from any one of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, aryl or heteroaryl substituted amine; n is an integer of 0 to 6; all groups may be partially deuterated or fully deuterated.
2. The composition as claimed in claim 1, wherein (L ^ Z) of the iridium metal complex of formula (I) is selected from one of the following representative structural formulae:
Figure FDA0003668602610000021
wherein Y is selected from O or N; R1-R3 are independently selected from C1-C18 alkyl, C1-C18 alkoxy, alkyl silicon group containing C1-C18, alkoxy silicon group containing C1-C18, aryl group containing C6-C40 or heteroaryl group containing C1-C40; a2 and B2 are selected from C1-C60 alkyl, C1-C60 alkoxy, C1-C60 alkylsilyl, C1-C60 alkoxysilyl, C6-C40 aryl or C1-C40 heteroaryl, wherein the ring of A2 and B2 is formed or not formed, A2 and B2 can be mono-substituted or poly-substituted according to valence principle, and all the groups can be partially deuterated or fully deuterated.
3. The composition as claimed in any one of claims 1 to 2, wherein (lz) in the iridium metal complex of formula (I) is selected from one of the following representative structural formulae:
Figure FDA0003668602610000022
wherein X is selected from NR1, O, S, CR1R2, SiR1R2, O ═ P-R1, or B-R1; R1-R3 are independently selected from C1-C18 alkyl, C1-C18 alkoxy, alkyl silicon group containing C1-C18, alkoxy silicon group containing C1-C18, aryl group containing C6-C40 or heteroaryl group containing C1-C40, and can be partially deuterated or fully deuterated.
4. The composition as claimed in any one of claims 1 to 2, wherein the iridium metal complex of formula (I) is selected from the following representative structures:
Figure FDA0003668602610000031
Figure FDA0003668602610000041
Figure FDA0003668602610000051
Figure FDA0003668602610000061
Figure FDA0003668602610000071
Figure FDA0003668602610000081
Figure FDA0003668602610000091
Figure FDA0003668602610000101
Figure FDA0003668602610000111
Figure FDA0003668602610000121
Figure FDA0003668602610000131
Figure FDA0003668602610000141
Figure FDA0003668602610000151
Figure FDA0003668602610000161
Figure FDA0003668602610000171
Figure FDA0003668602610000181
Figure FDA0003668602610000191
Figure FDA0003668602610000201
Figure FDA0003668602610000211
Figure FDA0003668602610000221
5. the composition of claim 1, wherein formula (II) is selected from the group consisting of compounds of II-1 to II-7:
Figure FDA0003668602610000231
wherein X1 to X6, L, A, B, R, n are the same as in claim 1.
6. The composition of claim 1, wherein a and B are selected from the group consisting of those described by the following structures:
Figure FDA0003668602610000232
wherein X1 to X6, Y1 to Y8, L, R, n are the same as recited in claim 1.
7. The composition according to any one of claims 1 to 2, wherein the organic compound of formula (II) or formula (III) is selected from one of the following representative structures:
Figure FDA0003668602610000241
Figure FDA0003668602610000251
Figure FDA0003668602610000261
Figure FDA0003668602610000271
Figure FDA0003668602610000281
Figure FDA0003668602610000291
Figure FDA0003668602610000301
Figure FDA0003668602610000311
Figure FDA0003668602610000321
Figure FDA0003668602610000331
Figure FDA0003668602610000341
Figure FDA0003668602610000351
Figure FDA0003668602610000361
Figure FDA0003668602610000371
Figure FDA0003668602610000381
Figure FDA0003668602610000391
Figure FDA0003668602610000401
Figure FDA0003668602610000411
Figure FDA0003668602610000421
Figure FDA0003668602610000431
Figure FDA0003668602610000441
Figure FDA0003668602610000451
Figure FDA0003668602610000461
Figure FDA0003668602610000471
Figure FDA0003668602610000481
Figure FDA0003668602610000491
Figure FDA0003668602610000501
Figure FDA0003668602610000511
Figure FDA0003668602610000521
Figure FDA0003668602610000531
Figure FDA0003668602610000541
Figure FDA0003668602610000551
Figure FDA0003668602610000561
Figure FDA0003668602610000571
Figure FDA0003668602610000581
Figure FDA0003668602610000591
Figure FDA0003668602610000601
Figure FDA0003668602610000611
Figure FDA0003668602610000621
Figure FDA0003668602610000631
Figure FDA0003668602610000641
Figure FDA0003668602610000651
Figure FDA0003668602610000661
Figure FDA0003668602610000671
Figure FDA0003668602610000681
Figure FDA0003668602610000691
Figure FDA0003668602610000701
Figure FDA0003668602610000711
Figure FDA0003668602610000721
Figure FDA0003668602610000731
Figure FDA0003668602610000741
Figure FDA0003668602610000751
Figure FDA0003668602610000761
Figure FDA0003668602610000771
Figure FDA0003668602610000781
Figure FDA0003668602610000791
Figure FDA0003668602610000801
Figure FDA0003668602610000811
8. a formulation comprising a composition according to any one of claims 1 to 7 and at least one solvent.
9. A formulation according to claim 8, wherein the composition and solvent form a formulation in which the solvent used is an unsaturated hydrocarbon solvent, a halogenated saturated hydrocarbon solvent, a halogenated unsaturated hydrocarbon solvent, an ether solvent or an ester solvent,
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.
10. 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 1 to 7.
11. The organic electroluminescent device according to claim 10, wherein the iridium metal complex and the organic compound are contained in a light-emitting layer, and wherein the mass percentage of the iridium metal complex is from 1% to 50%.
12. A display or lighting device comprising the organic electroluminescent element as claimed in any one of claims 10 to 11.
CN202011571801.5A 2020-12-27 2020-12-27 Composition and organic electroluminescent element comprising same Active CN112652731B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011571801.5A CN112652731B (en) 2020-12-27 2020-12-27 Composition and organic electroluminescent element comprising same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011571801.5A CN112652731B (en) 2020-12-27 2020-12-27 Composition and organic electroluminescent element comprising same

Publications (2)

Publication Number Publication Date
CN112652731A CN112652731A (en) 2021-04-13
CN112652731B true CN112652731B (en) 2022-07-22

Family

ID=75363139

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011571801.5A Active CN112652731B (en) 2020-12-27 2020-12-27 Composition and organic electroluminescent element comprising same

Country Status (1)

Country Link
CN (1) CN112652731B (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102103959B1 (en) * 2013-07-11 2020-04-28 삼성디스플레이 주식회사 Iridium complex and Organic light emitting device comprising the same
CN110574496B (en) * 2017-04-27 2022-01-11 住友化学株式会社 Composition and light-emitting element using same
KR102558986B1 (en) * 2017-04-27 2023-07-26 스미또모 가가꾸 가부시키가이샤 Composition and light emitting device using the same
US20200407386A1 (en) * 2017-04-27 2020-12-31 Sumitomo Chemical Company, Limited Composition and light emitting device using the same
CN108232022A (en) * 2017-12-29 2018-06-29 南京邮电大学 A kind of organic electroluminescence device and preparation method thereof
US11758802B2 (en) * 2019-03-29 2023-09-12 Samsung Electronics Co., Ltd. Composition and organic light-emitting device including the same
CN110698387A (en) * 2019-09-04 2020-01-17 宁波卢米蓝新材料有限公司 Fused ring compound and preparation method and application thereof

Also Published As

Publication number Publication date
CN112652731A (en) 2021-04-13

Similar Documents

Publication Publication Date Title
CN111995999B (en) Combination of deuterated guest compound and host compound and photoelectric device comprising same
CN112614964B (en) Composition and organic electroluminescent element comprising same
CN112680219B (en) Composition and organic electroluminescent element comprising same
CN112645985A (en) Iridium metal complex and organic photoelectric element using same
CN112724178A (en) Iridium metal compound with deuterium-fluorine synergistic effect and photoelectric element comprising iridium metal compound
CN112670426B (en) Composition and organic electroluminescent element comprising same
CN112851714A (en) Iridium metal complex and organic photoelectric element using same
CN112645987A (en) Iridium metal complex and organic photoelectric element using same
CN112694502A (en) Iridium metal complex and organic photoelectric element using same
CN112679552A (en) Iridium metal complex and organic photoelectric element using same
CN112645988A (en) Iridium metal complex and organic photoelectric element using same
CN112679550A (en) Iridium metal complex and organic photoelectric element using same
CN112652731B (en) Composition and organic electroluminescent element comprising same
CN112694501A (en) Iridium metal complex and organic photoelectric element using same
CN112687824B (en) Composition and organic electroluminescent element comprising same
CN112802970B (en) Composition and organic electroluminescent element comprising same
CN112713250B (en) Composition and organic electroluminescent element comprising same
CN112687819B (en) Composition and organic electroluminescent element comprising same
CN112687823B (en) Composition and organic electroluminescent element comprising same
CN112687822B (en) Composition and organic electroluminescent element comprising same
CN112652730B (en) Composition and organic electroluminescent element comprising same
CN112680217B (en) Composition and organic electroluminescent element comprising same
CN112608737A (en) Composition and organic electroluminescent element comprising same
CN113416536B (en) Host-guest composition and organic electroluminescent element comprising same
CN113421983B (en) Composition and organic electroluminescent element comprising same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant