CN108892689A - A kind of metal-organic complex and its organic electroluminescence device - Google Patents
A kind of metal-organic complex and its organic electroluminescence device Download PDFInfo
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- CN108892689A CN108892689A CN201810629425.7A CN201810629425A CN108892689A CN 108892689 A CN108892689 A CN 108892689A CN 201810629425 A CN201810629425 A CN 201810629425A CN 108892689 A CN108892689 A CN 108892689A
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- QOSSAOTZNIDXMA-UHFFFAOYSA-N C(CC1)CCC1N=C=NC1CCCCC1 Chemical compound C(CC1)CCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- PQNJZUJBNHNIFY-UHFFFAOYSA-N CC(C1)(C1C1C=CC=CC1)N(C)C1CCCCC1 Chemical compound CC(C1)(C1C1C=CC=CC1)N(C)C1CCCCC1 PQNJZUJBNHNIFY-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-O C[NH2+]C1CCCCC1 Chemical compound C[NH2+]C1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
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- 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
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
Abstract
The invention discloses a kind of metal-organic complex and its organic electroluminescence devices, are related to organic optoelectronic materials technology.The first ligand and assistant ligand in structure of the invention Formulas I being capable of better stable central metal atoms, simultaneously because five-membered ring configuration and quaternary ring configuration that the first ligand and Ligands are formed with metallic atom respectively make metal-organic complex have more rigid structure, high-performance, efficient phosphorescent emissions are realized.By introducing the substituent group of large volume, the glass transition temperature and thermal stability of metal-organic complex are effectively raised, material filming is conducive to.Organic electroluminescence device of the invention includes cathode, anode and one or more organic matter layers, at least one layer in organic matter layer contains metal-organic complex of the invention, organic electroluminescence device of the invention, with lower driving voltage, higher luminous efficiency and luminous brightness, and there is longer service life.
Description
Technical field
The present invention relates to organic photoelectrical material technical fields, and in particular to a kind of metal-organic complex and its organic electroluminescence
Luminescent device.
Background technique
Luminous organic material can substantially be divided into three according to principle of luminosity as a critical material in OLED device
Class：Conventional fluorescent material, phosphor material and hot activation delayed fluorescence (TADF) material.Conventional fluorescent material is only capable of utilizing 25%
Singlet excitons radioluminescence, luminous efficiency are lower.Phosphor material can utilize 25% singlet excitons and 75% triplet exciton
Radioluminescence theoretically can reach 100% internal quantum efficiency, and 1998, M.A.Baldo et al. is adulterated in luminescent layer to be contained
The organic chelated molecule PtOEt of transition metal platinum, prepares external quantum efficiency 4%, theoretical internal quantum efficiency can achieve 100%
Saturated red phosphorescent OLED device, this make theoretically electroluminescent internal quantum efficiency breach the upper of fluorescence efficiency 25%
Limit, then more and more phosphor materials for Organic Light Emitting Diode are developed, wherein mostly transition gold
Belong to ionic complex, causes in the application study of organic electroluminescent LED due to its efficient luminescent properties greatly
Pay attention to.And these metal complexs for being used as organic electroluminescent LED are mostly the gold of platinum (Pt), osmium (Os) and iridium (Ir)
Metal complex, wherein iridium metal complex is maximally efficient, usually contains the regular octahedron structure of positive trivalent oxidation state, high efficiency
Phosphorescence shine be due to metal complex configuration of extra-nuclear electron have strong SO coupling caused by.
Currently, usually there is the problems such as operation voltage is high, luminous efficiency is low, service life is short in organic electroluminescence device.
Thus, exploring the new organic photoelectrical material for organic electroluminescence device is that those skilled in the art study all the time
Emphasis direction.For luminescent layer, traditionally object dopant material used, can not usually provide the satisfactory spy that shines
Property, therefore, it is still necessary to design the better object dopant material of new performance to improve the service performance of organic electroluminescence device.
Summary of the invention
Goal of the invention：In view of the above-mentioned problems, the object of the present invention is to provide a kind of metal-organic complex and its Organic Electricities
Electroluminescence device, which applies in organic electroluminescence device as dopant material, to reduce
The driving voltage of organic electroluminescence devices, improves the luminous efficiency and brightness of organic electroluminescence device, and has extended
The service life of organic electroluminescence devices.
Above-mentioned technical purpose of the invention is achieved through the following technical solutions：A kind of metal-organic complex, this has
Organic metal complex has the general structure as shown in structural formula I：
Wherein, the X is selected from C (R4) or N, the R4Selected from hydrogen, the alkyl of substituted or unsubstituted C1~C20, substitution
Or one of the aryl of unsubstituted C6~C30, heteroaryl of substituted or unsubstituted C3~C30；
The X1、X2、X3、X4It is independent to be selected from C (R5) or N, the R5Selected from hydrogen, substituted or unsubstituted C1~C30
Alkyl, the aryl of substituted or unsubstituted C6~C60, one of the heteroaryl of substituted or unsubstituted C3~C60；
The R is selected from the alkyl of substituted or unsubstituted C1~C20, the aryl of substituted or unsubstituted C6~C30, substitution
Or one of heteroaryl of unsubstituted C3~C30；
The R1、R2The independent alkyl selected from substituted or unsubstituted C1~C30, substituted or unsubstituted C6~C60
One of aryl, heteroaryl of substituted or unsubstituted C3~C60；
The R3The aryl of alkyl, substituted or unsubstituted C6~C60 selected from substituted or unsubstituted C1~C30 takes
Group shown in the heteroaryl or Formula II of generation or unsubstituted C3~C60,
The R6、R7The independent alkyl selected from substituted or unsubstituted C1~C20, substituted or unsubstituted C6~C30
One of aryl, heteroaryl of substituted or unsubstituted C3~C30；
The M is transition metal.
Preferably, the M is selected from Ir, Rh, Re, Ru, Os, Pt, Au or Cu.
Preferably, the R4It does not take selected from hydrogen, methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substitution or
One of the phenyl in generation, substituted or unsubstituted furyl, substituted or unsubstituted thienyl；
The R5Selected from hydrogen, methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted benzene
One of base, substituted or unsubstituted furyl, substituted or unsubstituted thienyl.
Preferably, the R is selected from methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted
Phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substitution or not
Substituted pyridazinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted furyl, in substituted or unsubstituted thienyl
One kind.
Preferably, the R1、R2It is independent to be selected from methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substitution
Or unsubstituted phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted furans
One of base, substituted or unsubstituted thienyl.
Preferably, the R3Selected from methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted
Phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted carbazyl, substitution or
Unsubstituted dibenzofuran group, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted fluorenyl or Formula II institute
The group shown,
The R6、R7It is independent selected from methyl, it is ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted
Phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted furyl, substitution or
One of unsubstituted thienyl.
Preferably, M is selected from Ir.
Most preferably, metal-organic complex is selected from one of chemical structure as follows,
Further, the present invention also provides a kind of organic electroluminescence device, organic electroluminescence device include anode,
Cathode and one or more organic matter layers, the organic matter layer is between anode and cathode, in the organic matter layer extremely
Few one layer of metal-organic complex containing aforementioned present invention.
Preferably, organic matter layer includes luminescent layer, and the metal-organic complex of aforementioned present invention is used as the visitor in luminescent layer
Body material.
Beneficial effect：Compared with prior art, it is an advantage of the invention that organic metal shown in structure of the invention Formulas I
Complex compound includes the first ligand and assistant ligand, and the first ligand of the invention and assistant ligand being capable of better stable central metals
Atom, simultaneously because five-membered ring configuration and quaternary ring configuration that the first ligand and Ligands are formed with metallic atom respectively make to have
Organic metal complex has more rigid structure, can reduce unnecessary vibrational energy loss in molecule, can significantly drop
The phosphorescent lifetime of low complex compound realizes high-performance, efficient phosphorescence hair to reduce the generation of triplet state-triplet state annihilation
It penetrates.By the substituent group of introducing large volume, the glass transition temperature and thermal stability of metal-organic complex are effectively raised,
Be conducive to material filming.
Metal-organic complex of the invention is applied in organic electroluminescence device, especially as guest materials,
Organic electroluminescence device is set to show the advantages of driving voltage is low, luminous efficiency is high, light emission luminance is high and long service life,
Better than existing common OLED device.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after the present invention has been read, those skilled in the art are to various equivalences of the invention
The modification of form falls within the application range as defined in the appended claims.
A kind of metal-organic complex, the metal-organic complex have the general structure as shown in structural formula I：
Wherein, the X is selected from C (R4) or N, the R4Selected from hydrogen, the alkyl of substituted or unsubstituted C1~C20, substitution
Or one of the aryl of unsubstituted C6~C30, heteroaryl of substituted or unsubstituted C3~C30；
The X1、X2、X3、X4It is independent to be selected from C (R5) or N, the R5Selected from hydrogen, substituted or unsubstituted C1~C30
Alkyl, the aryl of substituted or unsubstituted C6~C60, one of the heteroaryl of substituted or unsubstituted C3~C60；
The R is selected from the alkyl of substituted or unsubstituted C1~C20, the aryl of substituted or unsubstituted C6~C30, substitution
Or one of heteroaryl of unsubstituted C3~C30；
The R1、R2The independent alkyl selected from substituted or unsubstituted C1~C30, substituted or unsubstituted C6~C60
One of aryl, heteroaryl of substituted or unsubstituted C3~C60；
The R3The aryl of alkyl, substituted or unsubstituted C6~C60 selected from substituted or unsubstituted C1~C30 takes
Group shown in the heteroaryl or Formula II of generation or unsubstituted C3~C60,
The R6、R7The independent alkyl selected from substituted or unsubstituted C1~C20, substituted or unsubstituted C6~C30
One of aryl, heteroaryl of substituted or unsubstituted C3~C30；
The M is transition metal.
Preferably, the M is selected from Ir, Rh, Re, Ru, Os, Pt, Au or Cu.
Preferably, the R4It does not take selected from hydrogen, methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substitution or
One of the phenyl in generation, substituted or unsubstituted furyl, substituted or unsubstituted thienyl；
The R5Selected from hydrogen, methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted benzene
One of base, substituted or unsubstituted furyl, substituted or unsubstituted thienyl.
Preferably, the R is selected from methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted
Phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substitution or not
Substituted pyridazinyl, substituted or unsubstituted triazine radical, substituted or unsubstituted furyl, in substituted or unsubstituted thienyl
One kind.
Preferably, the R1、R2It is independent to be selected from methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substitution
Or unsubstituted phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted furans
One of base, substituted or unsubstituted thienyl.
Preferably, the R3Selected from methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted
Phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted carbazyl, substitution or
Unsubstituted dibenzofuran group, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted fluorenyl or Formula II institute
The group shown,
The R6、R7It is independent selected from methyl, it is ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted
Phenyl, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted furyl, substitution or
One of unsubstituted thienyl.
Preferably, M is selected from Ir.
According to the present invention, the substituent group on abovementioned alkyl is independent selected from deuterium, cyano, halogen, the alkyl of C1~C10, C1
The heteroaryl of the alkoxy of~C10, the aryl of C6~C24 or C3~C24；
The independent alkane for being selected from deuterium, cyano, halogen, trifluoromethyl, C1~C10 of substituent group on above-mentioned aryl, heteroaryl
Base, the alkoxy of C1~C10, the aryl of C6~C24 or C3~C24 heteroaryl.
Alkyl of the present invention refers to alkyl made of minusing a hydrogen atom in alkane molecule, can be straight chain alkane
Base, branched alkyl, naphthenic base, example may include methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth
Base, amyl, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Aryl of the present invention refers to remove a hydrogen atom on the aromatic core carbon of aromatic hydrocarbon molecule after, be left the total of univalent perssad
Claiming, can be monocyclic aryl or fused ring aryl, example may include phenyl, xenyl, naphthalene, anthryl, phenanthryl or pyrenyl etc., but
It is without being limited thereto.
Heteroaryl of the present invention refers to the group that one or more aromatic core carbon in aryl are substituted by hetero atom
General name, the hetero atom include but is not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl or condensed ring heteroaryl
Base, example may include pyridyl group, pyrrole radicals, pyridyl group, thienyl, furyl, indyl, quinolyl, isoquinolyl, benzo thiophene
Pheno base, benzofuranyl, dibenzofuran group, dibenzothiophene, carbazyl etc., but not limited to this.
The alkyl of substituted or unsubstituted C1~C30 of the present invention, substituted or unsubstituted C6~C60 aryl, take
The heteroaryl of generation or unsubstituted C3~C60 refer to be substituted before alkyl, aryl, heteroaryl the total number of carbon atoms be respectively 1~
30,6~60,3~60, and so on.
Chain-like alkyl of the carbon atom numbers such as propyl of the present invention, butyl, amyl greater than two includes their isomers, such as
Isopropyl, isobutyl group, sec-butyl, tert-butyl, isopentyl, neopentyl, tertiary pentyl etc., but not limited to this.
As an example, it is not particularly limited, metal-organic complex of the invention is in chemical structure as follows
One kind,
The synthetic route of metal-organic complex of the invention is as follows：
Wherein, the X is selected from C (R4) or N, the R4Selected from hydrogen, the alkyl of substituted or unsubstituted C1~C20, substitution
Or one of the aryl of unsubstituted C6~C30, heteroaryl of substituted or unsubstituted C3~C30；
The X1、X2、X3、X4It is independent to be selected from C (R5) or N, the R5Selected from hydrogen, substituted or unsubstituted C1~C30
Alkyl, the aryl of substituted or unsubstituted C6~C60, one of the heteroaryl of substituted or unsubstituted C3~C60；
The R is selected from the alkyl of substituted or unsubstituted C1~C20, the aryl of substituted or unsubstituted C6~C30, substitution
Or one of heteroaryl of unsubstituted C3~C30；
The R1、R2The independent alkyl selected from substituted or unsubstituted C1~C30, substituted or unsubstituted C6~C60
One of aryl, heteroaryl of substituted or unsubstituted C3~C60；
The R3The aryl of alkyl, substituted or unsubstituted C6~C60 selected from substituted or unsubstituted C1~C30 takes
Group shown in the heteroaryl or Formula II of generation or unsubstituted C3~C60,
The R6、R7The independent alkyl selected from substituted or unsubstituted C1~C20, substituted or unsubstituted C6~C30
One of aryl, heteroaryl of substituted or unsubstituted C3~C30；
The M is transition metal.
In compound E, work as R3On be directly connected with singly-bound when being carbon atom, compound E is R3- Br works as R3On directly with
Singly-bound is connected when being nitrogen-atoms, and compound E is R3-H。
(1) under protection of argon gas, compound C, compound D, potassium carbonate, two (tri-terts are sequentially added into reaction flask
Phosphine) palladium, toluene, it stirred at reflux 5 hours, is cooled to room temperature, is extracted with toluene, wash, anhydrous sodium sulfate is dry, passes through column layer
Analysis purifying, obtains intermediate A.
(2) under nitrogen protection, intermediate A, MCl are sequentially added into flask3, pure water, flow back at 150 DEG C 12 small
When, stop reaction, distilled water is added, precipitating is precipitated, reaction mixture is filtered, dehydrated alcohol washs filter cake, obtains after drying
Mesosome B.
(3) it sequentially adds compound E, n-hexane into flask, at nitrogen protection and -78 DEG C, n-BuLi, stirring is added dropwise
Lower reaction one hour, is added dropwise compound F, room temperature is gradually increased to after being added dropwise to complete, stirring is lower, and the reaction was continued one hour, nitrogen protection
Under be slowly dropped in the hexane solution of intermediate B, be added dropwise, be to slowly warm up to 80 DEG C, react 8 hours, stop reaction,
Mixed liquor is cooled to room temperature, and decompression is spin-dried for solvent, and obtained solid product is washed three times with ether.Vacuum sublimation obtains structural formula I
Shown in product.
The synthetic route of metal-organic complex of the invention is not particularly limited, those skilled in the art can be used
Known popular response.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device include anode, cathode with
And one or more organic matter layers, between anode and cathode, at least one layer in organic matter layer contains above-mentioned organic matter layer
Metal-organic complex of the invention.
The organic matter layer of organic luminescent device of the invention have single layer structure, or optionally have two of them or
The multilayered structure of more organic matter layers layering.Organic electroluminescence device of the invention can have hole injection layer, hole to pass
Defeated layer, luminous material layer, electron transfer layer, electron injecting layer or the buffer layer being placed between anode and hole injection layer, which are used as, to be had
Machine nitride layer.However, the structure of organic electroluminescence device is without being limited thereto, but it may include small number of organic matter layer.Contain
The thickness of the organic matter layer of metal-organic complex of the invention is more preferably not higher than 6 μm, preferably not higher than 0.3 μm
0.002~0.3 μm.If desired, the organic matter layer containing metal-organic complex of the invention can further include this field
In known can be carried out hole injection, hole transport, luminous, electron-transport and electron injection other materials.
Organic electroluminescence device of the invention can be used known materials and be prepared by known methods, can at one layer or
It include metal-organic complex of the invention in multilayer organic matter layer.
Metal-organic complex of the invention specifically can be used as the visitor in the luminescent layer for preparing organic electroluminescence device
Body material.The organic electroluminescence device of use is preferably：ITO on transparent glass is attached to as anode, hole injection layer,
Hole transmission layer, light emitting host material：Metal-organic complex of the invention, electron transfer layer, electron injecting layer, metal yin
Pole.
Organic electroluminescence device of the invention can be widely applied to FPD, solid state lighting, Organophotoreceptor or have
The fields such as machine thin film transistor (TFT).
The present invention is not particularly limited raw material employed in following embodiment, can be for commercial product or using this
Preparation method known to the technical staff of field is prepared.
Embodiment 1：The preparation of compound TM1
Under protection of argon gas, sequentially added into reaction flask compound C1 (2.36g, 20mmol), compound D1 (9.24g,
44mmol), potassium carbonate (5.5g, 40mmol), two (tri-tert-butylphosphine) palladiums (20.4g, 0.04mmol), toluene (200ml), reflux
Lower stirring 5 hours, is cooled to room temperature, is extracted with toluene, washes, and anhydrous sodium sulfate is dry, by column chromatographic purifying, obtains centre
Body A1 (3.1g, 62%).
Under nitrogen protection, intermediate A 1 (3.0g, 12mmol), three hydrated iridium trichlorides are sequentially added into flask
(1.76g, 5mmol), pure water (5ml) flows back 12 hours at 150 DEG C, stops reaction, and distilled water 150ml is added and is precipitated and sinks
It forms sediment, reaction mixture is filtered, dehydrated alcohol washs filter cake, and intermediate B 1 is obtained after drying.
Sequentially add compound E1 (62.8mg, 0.4mmol), n-hexane (10ml) into flask, nitrogen protection and -78 DEG C
Under, the n-BuLi of the 2.6M of 0.15ml is added dropwise, stirs lower reaction one hour, is added dropwise compound F1 (50mg, 0.4mmol), drop
Room temperature is gradually increased to after the completion of adding, stirring is lower, and the reaction was continued one hour, and it is added to be slowly dropped to 15ml under nitrogen protection
It in the hexane solution of the intermediate B 1 of 0.2mmol, is added dropwise, is to slowly warm up to 80 DEG C, react 8 hours, stop reaction, mix
It closes liquid to be cooled to room temperature, decompression is spin-dried for solvent, and obtained solid product is washed three times with ether, each 20ml.Vacuum sublimation obtains
Compound TM1 (212mg, 60%).Mass spectrum m/z：Theoretical value：887.10；Measured value：889.62.Theoretical elemental content (%)
C45H42IrN8：C,60.93；H,4.77；Ir,21.67；N,12.63；It surveys constituent content (%)：C,60.91；H,4.82；Ir,
21.65；N,12.62.The above results confirm that obtaining product is target product.
Embodiment 2：The preparation of compound TM11
Change the compound D1 in embodiment 1 into equimolar compound D2, other steps with the synthesis phase of embodiment 1
Together, compound TM11 (262mg, 65%) is obtained.Mass spectrum m/z：Theoretical value：1011.25；Measured value：1013.52.Theoretical elemental
Content (%) C55H46IrN8：C,65.33；H,4.59；Ir,19.01；N,11.08；It surveys constituent content (%)：C,65.31；H,
4.65；Ir,19.00；N,11.05.The above results confirm that obtaining product is target product.
Embodiment 3：The preparation of compound TM16
Change the compound D1 in embodiment 1 into equimolar compound D3, compound F1 changes equimolar compound into
F2, other steps are identical as the synthesis of embodiment 1, obtain compound TM16 (298mg, 62%).Mass spectrum m/z：Theoretical value：
1203.59；Measured value：1205.73.Theoretical elemental content (%) C69H70IrN8：C,68.86；H,5.86；Ir,15.97；N,
9.31；It surveys constituent content (%)：C,68.83；H,5.92；Ir,15.95；N,9.30.The above results confirm that obtaining product is mesh
Mark product.
Embodiment 4：The preparation of compound TM35
Changing the compound C1 in embodiment 1 into equimolar C2, compound D1 changes equimolar compound D4 into, other
Step is identical as the synthesis of embodiment 1, obtains compound TM35 (254.6mg, 58%).Mass spectrum m/z：Theoretical value：
1097.38；Measured value：1098.42.Theoretical elemental content (%) C59H56IrN10：C,64.58；H,5.14；Ir,17.52；N,
12.76；It surveys constituent content (%)：C,64.55；H,5.21；Ir,17.50；N,12.74.The above results confirm that obtaining product is
Target product.
Embodiment 5：The preparation of compound TM72
Change the compound D1 in embodiment 1 into equimolar compound D5, compound E1 changes equimolar compound into
E2, compound F3 change equimolar compound F3 into, other steps are identical as the synthesis of embodiment 1, obtain compound TM72
(299.5mg, 62%).Mass spectrum m/z：Theoretical value：1207.62；Measured value：1208.32.Theoretical elemental content (%)
C69H74IrN8：C,68.63；H,6.18；Ir,15.92；N,9.28；It surveys constituent content (%)：C,68.61；H,6.24；Ir,
15.91；N,9.25.The above results confirm that obtaining product is target product.
Embodiment 6：The preparation of compound TM93
Change the compound C1 in embodiment 1 into equimolar compound C3, compound D1 changes equimolar compound into
D6, compound E1 change equimolar compound E3 into, other steps are identical as the synthesis of embodiment 1, obtain compound TM93
(253.2mg, 56%).Mass spectrum m/z：Theoretical value：1130.41；Measured value：1132.75.Theoretical elemental content (%)
C63H55IrN9：C,66.94；H,4.90；Ir,17.00；N,11.15；It surveys constituent content (%)：C,66.92；H,4.97；Ir,
16.97；N,11.13.The above results confirm that obtaining product is target product.
Embodiment 7：The preparation of compound TM114
Change the compound C1 in embodiment 1 into equimolar compound C3, compound D1 changes equimolar compound into
D7, compound E1 change equimolar compound E4 into, other steps are identical as the synthesis of embodiment 1, obtain compound TM114
(272.9mg, 59%).Mass spectrum m/z：Theoretical value：1156.45；Measured value：1157.52.Theoretical elemental content (%)
C65H57IrN9：C,67.51；H,4.97；Ir,16.62；N,10.90；It surveys constituent content (%)：C,67.48；H,5.05；Ir,
16.61；N,10.88.The above results confirm that obtaining product is target product.
Embodiment 8：The preparation of compound TM169
Change the compound C1 in embodiment 1 into equimolar compound C4, compound D1 changes equimolar compound into
D2, compound E1 change equimolar compound E5 into, other steps are identical as the synthesis of embodiment 1, obtain compound TM169
(231.7mg, 56%).Mass spectrum m/z：Theoretical value：1034.33；Measured value：1035.32.Theoretical elemental content (%)
C55H55IrN9：C,63.87；H,5.36；Ir,18.58；N,12.19；It surveys constituent content (%)：C,63.84；H,5.44；Ir,
18.56；N,12.16.The above results confirm that obtaining product is target product.
Other target products are synthesized referring to the synthetic method of above-described embodiment 1-8.
Application Example 1：The preparation of luminescent device 1
Selection ito glass is anode, dries after ultrasonic cleaning as in vacuum chamber, is evacuated to 5 × 10-5Pa, above-mentioned
Vacuum evaporation 2-TNATA is as hole injection layer, evaporation thickness 50nm in anode grid substrate.The vacuum evaporation on hole injection layer
NPB is as hole transmission layer, evaporation thickness 30nm.Vacuum evaporation CBP is as luminescent layer material of main part on the hole transport layer,
2% the compound of the present invention TM1 is as guest materials, evaporation thickness 30nm.The vacuum evaporation vacuum on luminous material layer
TPBi is deposited as electron transfer layer, evaporation thickness 30nm.Vapor deposition LiF is steamed as electron injecting layer on the electron transport layer
Plating is with a thickness of 0.5nm.Vacuum evaporation Al is as cathode, evaporation thickness 200nm on electron injecting layer.
Application Example 2：The preparation of luminescent device 2
Change the compound TM1 in Application Example 1 into compound TM11.
Application Example 3：The preparation of luminescent device 3
Change the compound TM1 in Application Example 1 into compound TM16.
Application Example 4：The preparation of luminescent device 4
Change the compound TM1 in Application Example 1 into compound TM35.
Application Example 5：The preparation of luminescent device 5
Change the compound TM1 in Application Example 1 into compound TM72.
Application Example 6：The preparation of luminescent device 6
Change the compound TM1 in Application Example 1 into compound TM93.
Application Example 7：The preparation of luminescent device 7
Change the compound TM1 in Application Example 1 into compound TM114.
Application Example 8：The preparation of luminescent device 8
Change the compound TM1 in Application Example 1 into compound TM169.
Comparative example 1
Selection ito glass is anode, dries after ultrasonic cleaning as in vacuum chamber, is evacuated to 5 × 10-5Pa, above-mentioned
Vacuum evaporation 2-TNATA is as hole injection layer, evaporation thickness 50nm in anode grid substrate.The vacuum evaporation on hole injection layer
NPB is as hole transmission layer, evaporation thickness 30nm.Vacuum evaporation CBP is as luminescent layer material of main part on the hole transport layer,
2% Ir (ppy)3As guest materials, evaporation thickness 30nm.Vacuum evaporation vacuum evaporation TPBi makees on luminous material layer
For electron transfer layer, evaporation thickness 30nm.As electron injecting layer, evaporation thickness is vapor deposition LiF on the electron transport layer
0.5nm.Vacuum evaporation Al is as cathode, evaporation thickness 200nm on electron injecting layer.
The characteristics of luminescence test result of luminescent device prepared by Application Example 1-8 of the present invention and comparative example 1 is such as
Shown in table 1.
Table 1
From table 1 it follows that metal-organic complex of the invention has been applied to as the guest materials in luminescent layer
In machine luminescent device, which shows lower driving voltage, higher luminous efficiency and longer uses the longevity
Life, and there is preferable durability and reliability.
Claims (10)
1. a kind of metal-organic complex, which is characterized in that the metal-organic complex has the structure as shown in structural formula I
General formula：
Wherein, the X is selected from C (R4) or N, the R4Selected from hydrogen, substituted or unsubstituted C1~C20 alkyl, replace or not
One of the aryl of substituted C6~C30, heteroaryl of substituted or unsubstituted C3~C30；
The X1、X2、X3、X4It is independent to be selected from C (R5) or N, the R5Alkane selected from hydrogen, substituted or unsubstituted C1~C30
One of base, the aryl of substituted or unsubstituted C6~C60, heteroaryl of substituted or unsubstituted C3~C60；
The R be selected from the alkyl of substituted or unsubstituted C1~C20, substituted or unsubstituted C6~C30 aryl, replace or not
One of substituted heteroaryl of C3~C30；
The R1、R2The virtue of the independent alkyl selected from substituted or unsubstituted C1~C30, substituted or unsubstituted C6~C60
One of base, heteroaryl of substituted or unsubstituted C3~C60；
The R3The aryl of alkyl, substituted or unsubstituted C6~C60 selected from substituted or unsubstituted C1~C30 replaces or not
Group shown in the heteroaryl or Formula II of substituted C3~C60,
The R6、R7The virtue of the independent alkyl selected from substituted or unsubstituted C1~C20, substituted or unsubstituted C6~C30
One of base, heteroaryl of substituted or unsubstituted C3~C30；
The M is transition metal.
2. a kind of metal-organic complex according to claim 1, which is characterized in that the M be selected from Ir, Rh, Re, Ru,
Os, Pt, Au or Cu.
3. a kind of metal-organic complex according to claim 1, which is characterized in that the R4Selected from hydrogen, methyl, ethyl,
Propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted furyl, substitution or not
One of substituted thienyl；
The R5Selected from hydrogen, methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted phenyl, take
One of generation or unsubstituted furyl, substituted or unsubstituted thienyl.
4. a kind of metal-organic complex according to claim 1, which is characterized in that the R is selected from methyl, ethyl, third
Base, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl group, substitution do not take
The pyrimidine radicals in generation, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, takes substituted or unsubstituted pyrazinyl
One of generation or unsubstituted furyl, substituted or unsubstituted thienyl.
5. a kind of metal-organic complex according to claim 1, which is characterized in that the R1、R2It is independent to be selected from first
Base, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl group,
One of substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted furyl, substituted or unsubstituted thienyl.
6. a kind of metal-organic complex according to claim 1, which is characterized in that the R3Selected from methyl, ethyl, third
Base, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl group, substitution do not take
The pyrimidine radicals in generation, substituted or unsubstituted carbazyl, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted hexichol
Group shown in bithiophene base, substituted or unsubstituted fluorenyl or Formula II,
The R6、R7It is independent to be selected from methyl, ethyl, propyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted benzene
Base, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted furyl, substitution do not take
One of the thienyl in generation.
7. a kind of metal-organic complex according to claim 1, which is characterized in that the M is selected from Ir.
8. a kind of metal-organic complex according to claim 1, which is characterized in that the metal-organic complex is selected from
One of chemical structure as follows：
9. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes anode, cathode and one
A or multiple organic matter layers, between anode and cathode, at least one layer in the organic matter layer contains the organic matter layer
Metal-organic complex described in claim 1-8 any one.
10. a kind of organic electroluminescence device according to claim 9, which is characterized in that the organic matter layer includes hair
Photosphere, metal-organic complex described in the claim 1-8 any one are used as the guest materials in luminescent layer.
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