CN108822154A - A kind of complex of iridium and its organic luminescent device - Google Patents
A kind of complex of iridium and its organic luminescent device Download PDFInfo
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- CN108822154A CN108822154A CN201810569980.5A CN201810569980A CN108822154A CN 108822154 A CN108822154 A CN 108822154A CN 201810569980 A CN201810569980 A CN 201810569980A CN 108822154 A CN108822154 A CN 108822154A
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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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
Abstract
The invention discloses a kind of complex of iridium and its organic luminescent devices, are related to organic optoelectronic materials technology.The complex of iridium has structure shown in formula (I), the dinitrogen coordination structure of electron rich in complex of iridium structure is conducive to stablize center trivalent metal cation, simultaneously, also it will affect the Cloud Distribution on metal iridium, and then the photoelectric property of entire complex molecule is had a huge impact, and the four-membered ring that the ligand of dinitrogen coordination structure and metal are constituted has stronger rigidity, advantageously reduces unnecessary vibrational energy loss, realizes efficient luminescent properties.By adjusting substituent group group, make complex that there is better thermal stability and chemical property.Complex of iridium is prepared into device, especially as dopant material, device shows the advantage that driving voltage is low, luminous efficiency is high, is better than existing common OLED device.
Description
Technical field
The present invention relates to organic photoelectrical material technical fields, and in particular to a kind of complex of iridium and its organic luminescent device.
Background technique
In recent years, organic electroluminescent LED (OLED) is due to excellent with ultra-thin, flexible, self-luminous, visual angular width etc.
Different characteristic is by favor.Wherein organic transitional complex (such as iridium, platinum) can pass through spin due to the presence of itself heavy atom
Coupling utilizes singlet and Triplet exciton simultaneously, theoretically realizes 100% internal quantum efficiency, causes everybody
Extensive concern.The dopant material in organic electroluminescence device luminescent layer still mainly uses phosphor material at present, wherein big absolutely
Part is organic coordination compound.
From Tang in 1987 et al. using 8-hydroxyquinoline aluminium (Alq3) as luminescent layer, it is highlighted low-voltage direct driving has been obtained
Organic electroluminescence device is spent, more and more organic coordination compounds for Organic Light Emitting Diode are developed.It is wherein red
The luminous organic coordination compound of color has Ir (piq)3、Ir(btpy)3、Ir(piq)2(acac), green emitting organic coordination compound has Ir
(ppy)3、Ir(ppy)2(acac)、Zn(BTZ)2、Ir(mppy)3, blue-light-emitting organic coordination compound material has FIrPic, Be
(PP)2, electron transport material Alq3, electron injection material Liq etc..
Organic coordination compound has the good characteristics of luminescence, wherein many complexs are in OLED and other electroluminescent technologies
It is widely studied in scientific research and industrial production, but still Shortcomings, the generally existing thermal stability of phosphor material is poor, luminous
Low efficiency, the high problem of driving voltage, and determine that the fundamental factor of organic electroluminescence device performance superiority and inferiority is the selection of material,
It would therefore be highly desirable to design and develop a kind of organic coordination compound low with higher luminous efficiency, driving voltage.
Summary of the invention
The object of the present invention is to provide a kind of complex of iridium and its organic luminescent device, complex of iridium tool provided by the invention
Have the advantages that driving voltage is low, luminous efficiency is high, is luminous organic material of good performance.Present invention firstly provides a kind of iridium to match
Object is closed, shown in general structure such as formula (I)：
Wherein, R1、R2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 alkane
One of oxygroup, substituted or unsubstituted C6~C25 aryl, substituted or unsubstituted C3~C18 heteroaryl；
R3Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 alkoxy, replace or not
The heteroaryl of the silylation of substituted C1~C10, substituted or unsubstituted C6~C25 aryl, substituted or unsubstituted C3~C18
One of base, amido of substituted or unsubstituted C2~C20；
R4-R11It does not take independently selected from hydrogen, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, substitution or
C1~C10 alkoxy in generation, substituted or unsubstituted C6~C25 aryl, one in substituted or unsubstituted C3~C18 heteroaryl
Kind；
X is selected from C (R12R13)、NR12、P(O)R12、PR12、S、SO、SO2、Si(R12R13) or O, wherein R12、R13Independently
Aryl, the substituted or unsubstituted C1 of alkyl, substituted or unsubstituted C6~C25 selected from substituted or unsubstituted C1~C10
One of the alkoxy of~C10.
Preferably, X is selected from C (R12R13)、NR12, S or O, wherein R12、R13Independently selected from methyl, ethyl, propyl, different
One of propyl, tert-butyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted phenyl.
Preferably, R1、R2Independently selected from methyl, ethyl, propyl, isopropyl, tert-butyl, cyclohexyl, phenyl, xenyl,
One of naphthalene.
Preferably, R3Selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, trimethylsilyl, phenyl, xenyl,
One of naphthalene, amido, fluorenyl, carbazyl, acridinyl.
Preferably, R4-R11Independently selected from hydrogen, cyano, halogen atom or substituted or unsubstituted following group：C1~C6
Alkyl, phenyl, naphthalene, anthryl, phenanthryl, pyrenyl, fluorenyl, two fluorenyl of spiral shell, carbazyl, pyridyl group, pyrimidine radicals, triazine radical, pheno thiophene
Piperazine base, phenoxazine group, acridinyl, dibenzothiophene, dibenzofuran group, benzothienyl, benzofuranyl, quinolyl or
One of isoquinolyl.
Preferably, any one of the complex of iridium in structure as follows：
The present invention also provides a kind of application of above-mentioned complex of iridium in an organic light emitting device.
Preferably, the organic luminescent device includes that anode, cathode and several between anode and cathode have
Machine functional layer, the organic function layer contain a kind of complex of iridium.
Preferably, a kind of organic luminescent device, the organic function layer include hole injection layer, hole transport
Layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, at least one layer in electron injecting layer；The luminescent layer
In at least contain a kind of complex of iridium.
Beneficial effects of the present invention：
The present invention provides a kind of complex of iridium, which has structure shown in formula (I), the richness in complex of iridium structure
The dinitrogen coordination structure of electronics is conducive to stablize center trivalent metal cation, and the ligand of dinitrogen coordination structure and metal structure
At four-membered ring have stronger rigidity, to obtain higher chemical stability and thermal stability.
Meanwhile this rigid structure advantageously reduces unnecessary vibrational energy loss, effectively reduces triplet excitons
Bury in oblivion, realize efficient luminescent properties, and the luminous efficiency of complex is greatly improved.
By introducing dinitrogen coordination structure, replace in traditional complex using the auxiliary such as pentanedione (acac) derivative
The hexa-atomic ring configuration that ligand and central metal atom are formed, it is connected with azepine carbazyl, so that obtaining a series of has
Completely new molecular structure.On the one hand conjugated system is increased, on the other hand makes charge more dispersed, improves the stabilization of the material
Property.
By adjusting molecular weight, to improve the glass transition temperature of material and be not easy to crystallize, and can drop low molecular flat
Face property is easy to form a film.
Complex of iridium preparation method of the present invention is simple, and raw material is easy to get, and can satisfy industrialization demand.
This complex of iridium is prepared into organic luminescent device, especially as dopant material, device shows driving electricity
It forces down, the advantage that luminous efficiency is high, is better than existing common OLED device.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
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.
Alkoxy of the present invention refer to alkyl and oxygen atom connection after group, example may include methoxyl group, ethyoxyl,
2- propoxyl group, 2- cyclohexyloxy 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, pyrimidine radicals, thienyl, furyl, indyl, quinolyl, isoquinolyl, benzo thiophene
Pheno base, benzofuranyl, dibenzofuran group, dibenzothiophene, carbazyl etc., but not limited to this.
Amido of the present invention refers to be made of a nitrogen-atoms and two hydrogen atoms, can be alkylamino radical or arylamine
Base, example may include-N (CH3)2、-N(CH2CH3)2With-N (ph)2Deng, but not limited to this.
After silylation of the present invention refers to that silane removes a hydrogen atom, remaining univalent perssad can be replaced by alkyl,
Example may include-Si (CH3)3Deng, but not limited to this.
Substituted alkyl of the present invention, substituted alkoxy, substituted aryl, substituted heteroaryl, substituted amido,
The substituent group independently selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthalene, anthryl, phenanthryl, benzo phenanthryl,
Base, pyrenyl, benzyl, methoxyl group, methyl mercapto, phenoxy group, thiophenyl, fluorenyl, 9,9- dimethyl fluorenyl, hexichol amido, diformazan
Amido, carbazyl, 9- phenyl carbazole base, furyl, thienyl, cyano, halogen atom, deuterium base, triphenyl silicon substrate, trimethyl silicane
Base, trifluoromethyl, phenothiazinyl, phenoxazine group, acridinyl, piperidyl, pyridyl group, pyrazinyl, triazine radical, pyrimidine radicals, biphenyl
Base, terphenyl, nitro etc., but not limited to this.
Present invention firstly provides a kind of complexs, shown in general structure such as formula (I)：
Wherein, R1、R2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 alkane
One of oxygroup, substituted or unsubstituted C6~C25 aryl, substituted or unsubstituted C3~C18 heteroaryl；
R3Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 alkoxy, replace or not
The heteroaryl of the silylation of substituted C1~C10, substituted or unsubstituted C6~C25 aryl, substituted or unsubstituted C3~C18
One of base, amido of substituted or unsubstituted C2~C20；
R4-R11It does not take independently selected from hydrogen, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, substitution or
C1~C10 alkoxy in generation, substituted or unsubstituted C6~C25 aryl, one in substituted or unsubstituted C3~C18 heteroaryl
Kind；
X is selected from C (R12R13)、NR12、P(O)R12、PR12、S、SO、SO2、Si(R12R13) or O, wherein R12、R13Independently
Aryl, the substituted or unsubstituted C1 of alkyl, substituted or unsubstituted C6~C25 selected from substituted or unsubstituted C1~C10
One of the alkoxy of~C10.
Preferably, X is selected from C (R12R13)、NR12, S or O, wherein R12、R13Independently selected from methyl, ethyl, propyl, different
One of propyl, tert-butyl, butyl, amyl, cyclopenta, cyclohexyl, substituted or unsubstituted phenyl.
Preferably, R1、R2Independently selected from methyl, ethyl, propyl, isopropyl, tert-butyl, cyclohexyl, phenyl, xenyl,
One of naphthalene.
Preferably, R3Selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, trimethylsilyl, phenyl, xenyl,
One of naphthalene, amido, fluorenyl, carbazyl, acridinyl.
Preferably, R4-R11Independently selected from hydrogen, cyano, halogen atom or substituted or unsubstituted following group：C1~C6
Alkyl, phenyl, naphthalene, anthryl, phenanthryl, pyrenyl, fluorenyl, two fluorenyl of spiral shell, carbazyl, pyridyl group, pyrimidine radicals, triazine radical, pheno thiophene
Piperazine base, phenoxazine group, acridinyl, dibenzothiophene, dibenzofuran group, benzothienyl, benzofuranyl, quinolyl or
One of isoquinolyl.
Most preferably, a kind of complex, any one of the complex of iridium in structure as follows：
A kind of some specific structure types of complex of iridium of the present invention are enumerated above, but the present invention does not limit to
All based on structure shown in formula (I) in these listed chemical structures, R is that group as defined above all should include
Inside.
A kind of complex of iridium of the invention, preparation method are as follows:
Wherein, R1、R2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 alkane
One of oxygroup, substituted or unsubstituted C6~C25 aryl, substituted or unsubstituted C3~C18 heteroaryl；
R3Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 alkoxy, replace or not
The heteroaryl of the silylation of substituted C1~C10, substituted or unsubstituted C6~C25 aryl, substituted or unsubstituted C3~C18
One of base, amido of substituted or unsubstituted C2~C20；
R4-R11It does not take independently selected from hydrogen, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, substitution or
C1~C10 alkoxy in generation, substituted or unsubstituted C6~C25 aryl, one in substituted or unsubstituted C3~C18 heteroaryl
Kind；
X is selected from C (R12R13)、NR12、P(O)R12、PR12、S、SO、SO2、Si(R12R13) or O, wherein R12、R13Independently
One of the aryl of alkyl, C6~C25 selected from C1~C10, alkoxy of C1~C10.
According to the present invention, intermediate A, B are prepared according to method as follows：
Compound a is dissolved in tetrahydrofuran, and after hexane solvent and n-BuLi is added dropwise, trimethylborate is slowly added dropwise,
Stirring neutralizes, extraction product.Compound b is recrystallized to give with methylene chloride and hexane.Under nitrogen protection, four triphenylphosphine
Palladium is that catalyst reacts compound b with bromo-derivative c in the case that potassium carbonate is alkali, and carbon carbon coupling reaction occurs and obtains centre
Body A.Under nitrogen protection, it reacts to obtain target product intermediate B in cellosolvo solvent with hydrated iridium trichloride.
According to the present invention, compound (I) is prepared according to method as follows：
N-BuLi is added dropwise in the hexane solution of bromo-derivative, diolefin compound is added dropwise again later to obtain intermediate
C.Intermediate B reacts to obtain target product compound (I) with intermediate C.
The present invention does not have special limitation to the coupling reaction, using coupling reaction well-known to those skilled in the art
, the preparation method is simple, and raw material is easy to get.
The present invention also provides a kind of application of above-mentioned complex of iridium in an organic light emitting device, a kind of iridium cooperation of the invention
Object can be used as emitting layer material and be applied in terms of organic luminescent device, and the organic luminescent device includes anode, cathode
And organic function layer, organic function layer include hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole barrier
Layer, electron transfer layer, at least one layer in electron injecting layer；At least matching containing a kind of iridium described above in the luminescent layer
Close object.Organic luminescent device of the invention shows in flat panel, planar illuminant, illumination face illuminating OLED illuminator, soft
Property illuminator, duplicator, printer, LCD backlight lamp or light source, display board, the mark of dosing machine class etc. are widely used.
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 1
The preparation of intermediate A 1
Compound a 1-2,6 dibromophenols (9.47g, 37.6mmol) are dissolved in tetrahydrofuran (140mL), in -78 DEG C of items
After hexane solvent and 2.5M n-BuLi (18mL, 45.1mmol) is added dropwise under part, stir 1 hour.Boric acid front three is slowly added dropwise again
After ester (13mL, 56.4mmol), 2h is stirred.2M hydrochloric acid is added dropwise again to neutralize, extract product with ethyl acetate and water.Use dichloromethane
Alkane and hexane are recrystallized to give compound b1 (4.10g, 47%).Weigh Compound b1 (5.82g, 25.1mmol), compound c1
(7.13g, 25.1mmol), tetra-triphenylphosphine palladium (11g, 10mmol) and potassium carbonate (8.42g, 60.9mmol), will be weighed anti-
Object is answered to be dissolved in toluene (1L)/EtOH (200mL)/distilled water (200mL) solvent, 90 DEG C are heated 2 hours.Weigh Compound
D1 (12.50g, 38mmol) is added KOH and Cu powder, and is reacted in 200 DEG C of heating, obtains compound e1.
It equally takes compound f1 (5.94g, 37.6mmol) to be dissolved in tetrahydrofuran (140mL), is dripped under the conditions of -78 DEG C
After adding hexane solvent and 2.5M n-BuLi (18mL, 45.1mmol), stir 1 hour.Trimethylborate is slowly added dropwise again
After (13mL, 56.4mmol), 2h is stirred.2M hydrochloric acid is added dropwise again to neutralize, extract product with ethyl acetate and water.Use methylene chloride
Compound g1 (3.56g, 77%) is recrystallized to give with hexane.Weigh Compound g1 (3.09g, 25.1mmol), compound e1
(6.23g, 25.1mmol), tetra-triphenylphosphine palladium (11g, 10mmol) and potassium carbonate (8.42g, 60.9mmol), will be weighed anti-
Object is answered to be dissolved in toluene (1L)/EtOH (200mL)/distilled water (200mL) solvent, 90 DEG C are heated 2 hours.Reaction terminate with
After be concentrated under reduced pressure, be extracted with ethyl acetate and be concentrated again, chromatographed to obtain intermediate A 1 (4.02g, 65%) with column.
The preparation of intermediate B 1
In 1L there-necked flask, be added hydrated iridium trichloride (14.11g, 40mmol) and intermediate A 1 (48.85g,
170mmol), 300mL2- ethoxy ethanol and 100mL water is then added, mixture is refluxed overnight in a nitrogen atmosphere.Reaction
After, it is cooled to room temperature, precipitating is filtered and is washed with methanol, intermediate B 1 (25.85g, yield 90%) is dried to obtain.
Mass spectrum m/z：1434.16 (calculated value：1434.15).Theoretical elemental content (%) C64H36Cl2Ir2N8O4：C,
53.52；H,2.53；Cl,4.94；Ir,26.76；N,7.80；O, 4.46 actual measurements constituent content (%)：C,53.53；H,2.53；
Cl,4.93；Ir,26.76；N,7.80；O,4.46.The above results confirm that obtaining product is target product.
The preparation of compound 1
The hexane solution (100mL) of h1- bromobenzene (3.1g, 20mmol) is added in 100mL four-hole boiling flask, be cooled to-
It 80 DEG C, is added dropwise n-BuLi (20mmol) under nitrogen atmosphere, after stirring 1.5 hours, N is added dropwise into mixed liquor, N '-two is different
Propyl carbodiimide (2.5g, 20mmol) after being added dropwise, continues stirring 2 hours, obtains yellow solution, this solution is dripped
It adds in tetrahydrofuran (100mL) solution of intermediate B 1 (10mmol), after being added dropwise, is warming up to 60 DEG C, stirs 12 hours,
Reaction solution is cooled to room temperature, and has a solid appearance, filter and with washed with ether filter cake three times, then dissolved with methylene chloride, concentration
Column chromatography, obtains compound 1 (5.51g, 30%).
Mass spectrum m/z：919.34 (calculated values：919.33).Theoretical elemental content (%) C47H46IrN6O2：C,61.42；H,
5.04；Ir,20.91；N,9.14；O, 3.48 actual measurements constituent content (%)：C,61.43；H,5.04；Ir,20.91；N,9.14；O,
3.47.The above results confirm that obtaining product is target product.
Embodiment 2：The preparation of compound 6
Change the c1 in embodiment 1 into equimolar c6, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 6 (5.49g, 29%).
Mass spectrum m/z：915.31 (calculated values：915.30).Theoretical elemental content (%) C47H42IrN6O2：C,61.69；H,
4.63；Ir,21.00；N,9.18；O, 3.50 actual measurements constituent content (%)：C,61.69；H,4.62；Ir,21.00；N,9.19；O,
3.50.The above results confirm that obtaining product is target product.
Embodiment 3：The preparation of compound 13
Change the f1 in embodiment 1 into equimolar f13, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 13 (5.49g, 29%).
Mass spectrum m/z：915.31 (calculated values：915.30).Theoretical elemental content (%) C47H42IrN6O2：C,61.69；H,
4.63；Ir,21.00；N,9.18；O, 3.50 actual measurements constituent content (%)：C,61.69；H,4.62；Ir,21.00；N,9.19；O,
3.50.The above results confirm that obtaining product is target product.
Embodiment 4：The preparation of compound 19
Change the f1 in embodiment 1 into equimolar f19, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 19 (6.00g, 28%).
Mass spectrum m/z：1071.40 (calculated value：1071.39).Theoretical elemental content (%) C59H54IrN6O2：C,66.15；H,
5.08；Ir,17.94；N,7.84；O, 2.99 actual measurements constituent content (%)：C,66.16；H,5.08；Ir,17.94；N,7.84；O,
2.98.The above results confirm that obtaining product is target product.
Embodiment 5：The preparation of compound 22
Change the f1 in embodiment 1 into equimolar f22, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 22 (6.33g, 27%).
Mass spectrum m/z：1171.44 (calculated value：1171.43).Theoretical elemental content (%) C67H58IrN6O2：C,68.70；H,
4.99；Ir,16.41；N,7.17；O, 2.73 actual measurements constituent content (%)：C,68.70；H,4.98；Ir,16.40；N,7.17；O,
2.73.The above results confirm that obtaining product is target product.
Embodiment 6：The preparation of compound 23
Change the f1 in embodiment 1 into equimolar f23, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 23 (5.83g, 28%).
Mass spectrum m/z：1041.33 (calculated value：1041.32).Theoretical elemental content (%) C55H44IrN8O2：C,63.44；H,
4.26；Ir,18.46；N,10.76；O, 3.07 actual measurements constituent content (%)：C,63.45；H,4.25；Ir,18.47；N,10.75；
O,3.07.The above results confirm that obtaining product is target product.
Embodiment 7：The preparation of compound 25
Change the f1 in embodiment 1 into equimolar f25, bromobenzene changes equimolar isopropyl bromide into, other steps with
The synthesis of embodiment 1 is identical, obtains target product compound 25 (5.72g, 31%).
Mass spectrum m/z：923.26 (calculated values：923.25).Theoretical elemental content (%) C45H36F2IrN6O2：C,58.56；H,
3.93；F,4.12；Ir,20.82；N,9.10；O, 3.47 actual measurements constituent content (%)：C,58.57；H,3.92；F,4.12；Ir,
20.83；N,9.10；O,3.46.The above results confirm that obtaining product is target product.
Embodiment 8：The preparation of compound 45
Change the h1 in embodiment 1 into equimolar h45, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 45 (5.31g, 30%).
Mass spectrum m/z：885.36 (calculated values：885.35).Theoretical elemental content (%) C44H48IrN6O2：C,59.71；H,
5.47；Ir,21.72；N,9.49；O, 3.62 actual measurements constituent content (%)：C,59.70；H,5.47；Ir,21.72；N,9.48；O,
3.62.The above results confirm that obtaining product is target product.
Embodiment 9：The preparation of compound 48
Change the h1 in embodiment 1 into equimolar h48, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 48 (5.87g, 30%).
Mass spectrum m/z：978.32 (calculated values：978.31).Theoretical elemental content (%) C51H43IrN7O2：C,62.62；H,
4.43；Ir,19.65；N,10.02；O, 3.27 actual measurements constituent content (%)：C,62.63；H,4.43；Ir,19.65；N,10.02；
O,3.26.The above results confirm that obtaining product is target product.
Embodiment 10：The preparation of compound 50
Change the h1 in embodiment 1 into equimolar h50, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 50 (5.66g, 29%).
Mass spectrum m/z：976.31 (calculated values：976.30).Theoretical elemental content (%) C51H41IrN7O2：C,62.75；H,
4.23；Ir,19.69；N,10.04；O, 3.28 actual measurements constituent content (%)：C,62.76；H,4.23；Ir,19.69；N,10.04；
O,3.27.The above results confirm that obtaining product is target product.
Embodiment 11：The preparation of compound 65
By the N in embodiment 1, N '-diisopropylcarbodiimide changes equimolar N into, N '-dicyclohexylcarbodiimide,
Other steps are identical as the synthesis of embodiment 1, obtain target product compound 65 (5.80g, 30%)
Mass spectrum m/z：967.20 (calculated values：967.19).Theoretical elemental content (%) C51H46IrN6O2：C,63.33；H,
4.79；Ir,19.87；N,8.69；O, 3.31 actual measurements constituent content (%)：C,63.34；H,4.79；Ir,19.87；N,8.69；O,
3.30.The above results confirm that obtaining product is target product.
Embodiment 12：The preparation of compound 66
By the N in embodiment 1, N '-diisopropylcarbodiimide changes equimolar N into, N '-diethyl carbodiimide,
His step is identical as the synthesis of embodiment 1, obtains target product compound 66 (5.52g, 31%).
Mass spectrum m/z：891.31 (calculated values：891.30).Theoretical elemental content (%) C45H42IrN6O2：C,60.66；H,
4.75；Ir,21.57；N,9.43；O, 3.59 actual measurements constituent content (%)：C,60.67；H,4.75；Ir,21.57；N,9.43；O,
3.58.The above results confirm that obtaining product is target product.
Embodiment 13：The preparation of compound 69
The preparation of intermediate A 69
Compound a 69 (10.56g, 37.6mmol) is dissolved in tetrahydrofuran (140mL), oneself is added dropwise under the conditions of -78 DEG C
After alkane solvents and 2.5M n-BuLi (18mL, 45.1mmol), stir 1 hour.Again slowly be added dropwise trimethylborate (13mL,
After 56.4mmol), 2h is stirred.2M hydrochloric acid is added dropwise again to neutralize, extract product with ethyl acetate and water.With methylene chloride and hexane
It is recrystallized to give compound b69 (4.33g, 47%).Weigh Compound b69 (9.10g, 37mmol), compound c69 (5.85g,
37mmol), tetra-triphenylphosphine palladium (11g, 10mmol) and potassium carbonate (8.42g, 60.9mmol), weighed reactant is dissolved in
In toluene (1L)/EtOH (200mL)/distilled water (200mL) solvent, 90 DEG C are heated 2 hours.Weigh Compound d69
Triethyl phosphite (200mL) and dichloro-benzenes (150mL) is added in (21.76g, 78mmol), stirs 12 hours at 150 DEG C, instead
It is concentrated under reduced pressure after should terminating, is extracted with ethyl acetate and is concentrated again, chromatographed to obtain intermediate e69 (10.60g, 55%) with column.
Weigh intermediate e69 (10.14g, 41mmol), compound f69 (7.06g, 41.5mmol), cuprous iodide (3.9g,
20.5mmol), ethylenediamine (1.4mL, 20.5mmol) and cesium carbonate (40g, 123mmol), and toluene is added to by said sequence
In (250mL), it is refluxed.It vacuum distillation, methylene chloride and hexane is extracted with ethyl acetate crosses pillar and obtain compound g69
(9.84g, 83%).
It equally takes compound f1 (5.94g, 37.6mmol) to be dissolved in tetrahydrofuran (140mL), is dripped under the conditions of -78 DEG C
After adding hexane solvent and 2.5M n-BuLi (18mL, 45.1mmol), stir 1 hour.Trimethylborate is slowly added dropwise again
After (13mL, 56.4mmol), 2h is stirred.2M hydrochloric acid is added dropwise again to neutralize, extract product with ethyl acetate and water.Use methylene chloride
Compound g1 (3.56g, 77%) is recrystallized to give with hexane.Weigh Compound g1 (3.09g, 25.1mmol), compound g69
(7.26g, 25.1mmol), tetra-triphenylphosphine palladium (11g, 10mmol) and potassium carbonate (8.42g, 60.9mmol), will be weighed anti-
Object is answered to be dissolved in toluene (1L)/EtOH (200mL)/distilled water (200mL) solvent, 90 DEG C are heated 2 hours.Reaction terminate with
After be concentrated under reduced pressure, be extracted with ethyl acetate and be concentrated again, chromatographed to obtain intermediate A 69 (3.97g, 55%) with column.
The preparation of intermediate B 69
In 1L there-necked flask, be added hydrated iridium trichloride (14.11g, 40mmol) and intermediate A 69 (48.85g,
170mmol), 300mL2- ethoxy ethanol and 100mL water is then added, mixture is refluxed overnight in a nitrogen atmosphere.Reaction
After, it is cooled to room temperature, precipitating is filtered and is washed with methanol, intermediate B 69 (28.81g, yield 90%) is dried to obtain.
Mass spectrum m/z：1666.57 (calculated value：1666.56).Theoretical elemental content (%) C76H64Cl2Ir2N12：C,57.02；
H,4.03；Cl,4.43；Ir,24.02；N, 10.50 actual measurements constituent content (%)：C,57.02；H,4.02；Cl,4.44；Ir,
24.02；N,10.50.The above results confirm that obtaining product is target product.
The preparation of compound 69
The hexane solution (100mL) of h1- bromobenzene (3.1g, 20mmol) is added in 100mL four-hole boiling flask, be cooled to-
It 80 DEG C, is added dropwise n-BuLi (20mmol) under nitrogen atmosphere, after stirring 1.5 hours, N is added dropwise into mixed liquor, N '-two is different
Propyl carbodiimide (2.5g, 20mmol) after being added dropwise, continues stirring 2 hours, obtains yellow solution, this solution is dripped
It adds in tetrahydrofuran (100mL) solution of intermediate B 69 (10mmol), after being added dropwise, is warming up to 60 DEG C, stirring 12 is small
When, reaction solution is cooled to room temperature, and has a solid appearance, filter and with washed with ether filter cake three times, then dissolved with methylene chloride, it is dense
Contracting column chromatography, obtains compound 69 (5.48g, 29%).
Mass spectrum m/z：945.40 (calculated values：945.39).Theoretical elemental content (%) C49H52IrN8：C,62.26；H,
5.55；Ir,20.34；N, 11.85 actual measurements constituent content (%)：C,62.26；H,5.56；Ir,20.33；N,11.85.Above-mentioned knot
Fruit confirms that obtaining product is target product.
Compare Application Example 1
Ito glass substrate is placed in distilled water and is cleaned 2 times, it is ultrasonic washing 15 minutes, different after distilled water cleans
Ultrasonic washing is later dry in order for propyl alcohol, acetone, methanol equal solvent, is transferred in plasma washing machine, by above-mentioned base
Plate washs 5 minutes, is sent in evaporator.
Hole injection layer 2-TNATA/50nm is successively deposited on the ito transparent electrode having had been prepared for, vapor deposition hole passes
Defeated layer NPB/30nm, vapor deposition main body CBP：It adulterates Ir (ppy)35% mixing/30nm, then vapor deposition electron transfer layer TPBi/
30nm, cathode LiF/0.5nm, Al/200nm.
[Application Example 1-13]
The Ir (ppy) in Application Example 1 will be compared3Change into shown compound 1 in Application Example 1-13,6,13,
19、22、23、25、45、48、50、65、66、69。
Table 1 is the compound of preparation of the embodiment of the present invention and the characteristics of luminescence test for comparing luminescent device prepared by substance
As a result.
The characteristics of luminescence of [table 1] luminescent device is tested
The above result shows that a kind of complex of iridium of the invention is applied in organic luminescent device, especially as luminous
Layer guest materials, shows the low advantage of high-luminous-efficiency, driving voltage, is luminous organic material of good performance.
Obviously, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should refer to
It out, without departing from the principle of the present invention, can also be to this hair for the those of ordinary skill of the technical field
Bright some improvement and modification can also be carried out, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (8)
1. a kind of complex of iridium, which is characterized in that shown in general structure such as formula (I)：
Wherein, R1、R2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 alkoxy,
One of substituted or unsubstituted C6~C25 aryl, substituted or unsubstituted C3~C18 heteroaryl；
R3Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 alkoxy, substituted or unsubstituted
The silylation of C1~C10, substituted or unsubstituted C6~C25 aryl, the heteroaryl of substituted or unsubstituted C3~C18, substitution
Or one of amido of unsubstituted C2~C20；
R4-R11Independently selected from hydrogen, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted
One of C1~C10 alkoxy, substituted or unsubstituted C6~C25 aryl, substituted or unsubstituted C3~C18 heteroaryl；
X is selected from C (R12R13)、NR12、P(O)R12、PR12、S、SO、SO2、Si(R12R13) or O, wherein R12、R13Independently selected from taking
Generation or the alkyl of unsubstituted C1~C10, the aryl of substituted or unsubstituted C6~C25, substituted or unsubstituted C1~C10
One of alkoxy.
2. a kind of complex of iridium according to claim 1, which is characterized in that X is selected from C (R12R13)、NR12, S or O, wherein
R12、R13Independently selected from methyl, ethyl, propyl, isopropyl, tert-butyl, butyl, amyl, cyclopenta, cyclohexyl, substitution or not
One of substituted phenyl.
3. a kind of complex of iridium according to claim 1, which is characterized in that R1、R2Independently selected from methyl, ethyl, third
One of base, isopropyl, tert-butyl, cyclohexyl, phenyl, xenyl, naphthalene.
4. a kind of complex of iridium according to claim 1, which is characterized in that R3Selected from methyl, ethyl, isopropyl, tertiary fourth
One of base, cyclohexyl, trimethylsilyl, phenyl, xenyl, naphthalene, amido, fluorenyl, carbazyl, acridinyl.
5. a kind of complex of iridium according to claim 1, which is characterized in that R4-R11Independently selected from hydrogen, cyano, halogen
Atom, substituted or unsubstituted following group：C1~C6 alkyl, phenyl, naphthalene, anthryl, phenanthryl, pyrenyl, fluorenyl, two fluorenes of spiral shell
Base, carbazyl, pyridyl group, pyrimidine radicals, triazine radical, phenothiazinyl, phenoxazine group, acridinyl, dibenzothiophene, dibenzo furan
It mutters one of base, benzothienyl, benzofuranyl, quinolyl or isoquinolyl.
6. a kind of complex of iridium according to claim 1, which is characterized in that the complex is in structure as follows
Any one：
7. a kind of organic luminescent device, including anode, cathode and several organic function layers between anode and cathode,
It is characterized in that, at least containing a kind of described in any item complex of iridium of claim 1~6 in the organic function layer.
8. a kind of organic luminescent device according to claim 7, which is characterized in that the organic function layer includes hole note
Enter layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer, in luminescent layer extremely
Contain a kind of described in any item complex of iridium of claim 1~6 less.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020066622A (en) * | 2018-09-15 | 2020-04-30 | 北京夏禾科技有限公司 | Metal complex containing fluorine substituted structure |
| CN112300216A (en) * | 2019-07-30 | 2021-02-02 | 环球展览公司 | Organic electroluminescent material and device |
| CN113278033A (en) * | 2020-02-20 | 2021-08-20 | 北京夏禾科技有限公司 | Organic electroluminescent material and device |
-
2018
- 2018-06-05 CN CN201810569980.5A patent/CN108822154A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020066622A (en) * | 2018-09-15 | 2020-04-30 | 北京夏禾科技有限公司 | Metal complex containing fluorine substituted structure |
| CN112300216A (en) * | 2019-07-30 | 2021-02-02 | 环球展览公司 | Organic electroluminescent material and device |
| EP3771717A1 (en) * | 2019-07-30 | 2021-02-03 | Universal Display Corporation | Organic electroluminescent materials and devices |
| EP4219515A1 (en) * | 2019-07-30 | 2023-08-02 | Universal Display Corporation | Organic electroluminescent materials and devices |
| CN113278033A (en) * | 2020-02-20 | 2021-08-20 | 北京夏禾科技有限公司 | Organic electroluminescent material and device |
| CN113278033B (en) * | 2020-02-20 | 2023-04-28 | 北京夏禾科技有限公司 | Organic electroluminescent material and device |
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