CN108570077A - A kind of organic coordination compound and its organic luminescent device containing metal - Google Patents
A kind of organic coordination compound and its organic luminescent device containing metal Download PDFInfo
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- CN108570077A CN108570077A CN201810569137.7A CN201810569137A CN108570077A CN 108570077 A CN108570077 A CN 108570077A CN 201810569137 A CN201810569137 A CN 201810569137A CN 108570077 A CN108570077 A CN 108570077A
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- 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
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Abstract
The invention discloses a kind of organic coordination compound and its organic luminescent device containing metal, is related to organic optoelectronic materials technology.The complex structure includes the first ligand and assistant ligand, wherein the first ligand has the recombination rate of certain electrophilic characteristic, raising hole and electronics in luminescent layer, to improve the luminous efficiency of organic luminescent device；The dinitrogen coordination structure of electron rich in assistant ligand structure is conducive to stablize center trivalent metal cation, simultaneously, also the Cloud Distribution on metal iridium can be influenced, and then the photoelectric property of entire complex molecule is had a huge impact, and the ligand of dinitrogen coordination structure has stronger rigidity with the four-membered ring that metal is constituted, unnecessary vibrational energy loss is advantageously reduced, realizes efficient luminescent properties.First ligand and assistant ligand are combined and are prepared into organic luminescent device, especially as dopant material, 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 organic coordination compound containing metal and its organic
Luminescent device.
Background technology
Organic compound is deposited the mode of Deng Qingyun of Kodak in 1987 et al. first passage vacuum evaporations
At unformed organic film, and different organic materials is selected to be prepared for double-deck OLED devices as hole and electron transfer layer
Part, for device when voltage is 10V or so, device light emission luminance has reached 1000cd m-2, maximum external quantum efficiency EQE
(External Quantum Efficiency) is 1% or so, shows extraordinary electroluminescent properties, this is indicated
Organic electroluminescence device (OLED) has had been provided with the possibility of practical application, from there on, each major company and scientific research machine
Structure has all put into the research that a large amount of manpower carries out organic electroluminescent direction with resource.Nineteen ninety univ cambridge uk
Friend et al. is prepared for being based on high molecular material poly (p-phenylene vinylene) by way of solution processing
(PPV) single layer OLED devices so that high molecular material is also gradually applied to field of organic electroluminescence.The general woods in the U.S. in 1998
The Forrest et al. of Si Dun universities reports the doping phosphorescent devices for object with octaethylporphyrin platinum (PtOEP).Be different from
Into fluorescent material, internal quantum efficiency is only 25% this limitation, and phosphor material realizes 100% internal quantum efficiency, phosphorescence electricity
An important breakthrough for being the discovery that electroluminescent organic material development for electroluminescent material.
In the latest 20 years, application of the phosphorescent light-emitting materials in organic electroluminescent receives academia and widely pays close attention to,
Relevant phosphorescent compound is contained with planar structure, the Pt (II) of d8 electron configurations, Pd (II), Au (III) complex, with
And with complexs such as octahedral structure, the Ru (II) of d6 electron configurations, Rh (III), Re (I), Ir (III), Os (II).Wherein
Study it is more be osmium, iridium, platinum and ruthenium complex, they have preferable luminous efficiency, and partly decline with shorter phosphorescence
Phase, to greatly reduce the probability that non-radiative mode fails.Complex of iridium is due to shorter phosphorescent lifetime, higher phosphorescence
Quantum yield, preferable thermal stability, regular octahedron coordination structure be not easy to form more serious pi-pi accumulation etc. it is excellent
Property becomes and designs new and effective feux rouges to an important research direction of near-infrared phosphor material.
Green light, the efficiency of yellow light organic phosphorescent material and service life can reach the requirement of industrialization substantially, but high property
The feux rouges phosphor material of energy still needs further to be developed.Metal iridium complex is due to, luminous efficiency shorter with phosphorescent lifetime
The advantages that high, simple, the photochromic easy adjusting of synthesis purification, good calorifics and electrochemical stability, it is new and effective to become design
One research hotspot of feux rouges phosphor material.
Currently, organic luminescent device develops towards practical, commercialization, but the brightness in device, efficiency and service life
On improved there is still a need for further, to organic material, higher requirements are also raised for this.How new performance better material is designed
Material is adjusted, and is always those skilled in the art's urgent problem to be solved.
Invention content
The object of the present invention is to provide a kind of organic coordination compound and its organic luminescent device containing metal, it is provided by the invention
Organic coordination compound containing metal has the advantages that driving voltage is low, luminous efficiency is high, is the luminous organic material of function admirable.
Present invention firstly provides a kind of organic coordination compound containing metal, structural formula (I) is：
Wherein, R1、R2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C25 virtues
One kind in base, substituted or unsubstituted C3~C18 heteroaryls；
R3Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 silylation, substitution or
The amido of unsubstituted C6~C25 aryl, the heteroaryl of substituted or unsubstituted C3~C18, substituted or unsubstituted C2~C20
In one kind；
R4-R7Independently selected from hydrogen, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, substitution or unsubstituted
C6~C25 aryl, one kind in substituted or unsubstituted C3~C18 heteroaryls；
M is selected from Ir；
RAOne kind in following group：
Preferably, the R1、R2Independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tertiary butyl, ring
One kind in hexyl, phenyl, xenyl, naphthalene.
Preferably, R3Selected from methyl, ethyl, isopropyl, tertiary butyl, cyclohexyl, trimethylsilyl, phenyl, xenyl,
One kind in naphthalene, amido, fluorenyl, carbazyl, acridinyl；
Preferably, R4-R7Independently 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 groups, acridinyl, dibenzothiophene, dibenzofuran group, benzothienyl, benzofuranyl, quinolyl or
One kind in isoquinolyl.
Preferably, any one of the organic coordination compound containing metal in structure as follows：
The present invention also provides a kind of application of the above-mentioned organic coordination compound containing metal in an organic light emitting device.
Preferably, the organic luminescent device, which includes anode, cathode and several between anode and cathode, has
Machine functional layer, the organic function layer contain a kind of organic coordination compound containing metal.
Preferably, a kind of organic luminescent device, the organic function layer include hole injection layer, hole transport
Layer, at least one layer in electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer；The luminescent layer
In at least contain a kind of organic coordination compound containing metal.
Beneficial effects of the present invention：
The present invention provides a kind of organic coordination compound and its organic luminescent device containing metal, which includes first
Ligand and assistant ligand, wherein the first ligand is by introducing big pi-conjugated structure and steric group, touching between reduction triplet excitons
It hits, overcomes the problems, such as that device efficiency under the high current density is roll-offed.
The dinitrogen coordination structure of electron rich in assistant ligand structure is conducive to stablize center trivalent metal cation, together
When, the Cloud Distribution on metal iridium can be also influenced, and then prodigious shadow is generated for the photoelectric property of entire complex molecule
It rings, and the ligand of dinitrogen coordination structure has stronger rigidity with the four-membered ring that metal is constituted, and advantageously reduces unnecessary
Vibrational energy loses, and realizes efficient luminescent properties.
By adjusting substituent group group, reference pyridine, pyrimidine, pyrazine, triazine, imidazoles, oxazole, thiazole, benzimidazole, benzene
And the heteroaryl groups such as oxazole, benzothiazole, quinoline, isoquinolin, quinoxaline can be effective with certain electrophilic characteristic
Improve the electron transport ability of material, improve hole and electronics luminescent layer recombination rate, to improve its organic luminescent device
Luminous efficiency.
Organic coordination compound using the present invention containing metal is prepared into organic luminescent device, especially as dopant material,
Device shows the advantage that driving voltage is low, luminous efficiency is high.
Organic coordination compound preparation method of the present invention containing metal is simple, and raw material is easy to get, and disclosure satisfy that industrialization demand.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are only the feature and advantage further illustrated 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 refers to alkyl and the group after oxygen atom connection, example may include methoxyl group, ethyoxyl,
2- propoxyl group, 2- cyclohexyloxies etc., but not limited to this.
Aryl of the present invention refer to aromatic hydrocarbon molecule aromatic core carbon on remove a hydrogen atom after, be left univalent perssad it is total
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 of aryl aromatic core carbon is substituted by hetero atom
General name, the hetero atom include but 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 being 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.
Silylation of the present invention refers to after silane removes a hydrogen atom, and 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, tertiary 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 carbazoles base, furyl, thienyl, cyano, halogen atom, deuterium base, triphenyl silicon substrate, trimethyl silicane
Base, trifluoromethyl, phenothiazinyl, phenoxazine groups, 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 organic coordination compound containing metal, structural formula (I) is：
Wherein, R1、R2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C25 virtues
One kind in base, substituted or unsubstituted C3~C18 heteroaryls；
R3Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 silylation, substitution or
The amido of unsubstituted C6~C25 aryl, the heteroaryl of substituted or unsubstituted C3~C18, substituted or unsubstituted C2~C20
In one kind；
R4-R7Independently selected from hydrogen, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, substitution or unsubstituted
C6~C25 aryl, one kind in substituted or unsubstituted C3~C18 heteroaryls；
M is selected from Ir；
RAOne kind in following group：
Preferably, the R1、R2Independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tertiary butyl, ring
One kind in hexyl, phenyl, xenyl, naphthalene.
Preferably, R3Selected from methyl, ethyl, isopropyl, tertiary butyl, cyclohexyl, trimethylsilyl, phenyl, xenyl,
One kind in naphthalene, amido, fluorenyl, carbazyl, acridinyl；
Preferably, R4-R7Independently 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 groups, acridinyl, dibenzothiophene, dibenzofuran group, benzothienyl, benzofuranyl, quinolyl or
One kind in isoquinolyl.
Preferably, any one of a kind of organic coordination compound containing metal in structure as follows：
Some specific structure types of the organic coordination compound of the present invention containing metal are enumerated above, but the present invention is simultaneously
These listed chemical constitutions are not limited to, every based on structure shown in formula (I), R is that group as defined above is all answered
This is included.
A kind of organic coordination compound containing metal of the present invention, preparation method are as follows：
Wherein, R1、R2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C25 virtues
One kind in base, substituted or unsubstituted C3~C18 heteroaryls；
R3Selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C1~C10 silylation, substitution or
The amido of unsubstituted C6~C25 aryl, the heteroaryl of substituted or unsubstituted C3~C18, substituted or unsubstituted C2~C20
In one kind；
R4-R7Independently selected from hydrogen, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, substitution or unsubstituted
C6~C25 aryl, one kind in substituted or unsubstituted C3~C18 heteroaryls；
M is selected from Ir；
RAOne kind in following group：
According to the present invention, intermediate A, intermediate B are prepared according to method as follows：
Under nitrogen protection, tetra-triphenylphosphine palladium is catalyst, in the case that potassium carbonate is alkali, by compound a and bromo
Object b reactions, occur carbon carbon coupling reaction and obtain compound c.Compound c is irradiated with toluene, iodine, and reaction generates compound d.
The life of carbon carbon coupling reaction occurs in the case where being alkali as catalyst potassium carbonate using tetra-triphenylphosphine palladium for compound d and compound e
At intermediate A.Under nitrogen protection, it is obtained by the reaction among target product in cellosolvo solvent with hydrated iridium trichloride
Body B.
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.Target product compound (I) is obtained by the reaction with intermediate C in intermediate B.
The present invention does not have the coupling reaction special limitation, using coupling reaction well-known to those skilled in the art
, the preparation method is simple, and raw material is easy to get.
It is of the invention the present invention also provides a kind of application of the above-mentioned organic coordination compound containing metal in an organic light emitting device
A kind of organic coordination compound containing metal can be applied as emitting layer material in terms of organic luminescent device, organic hair
Optical device includes anode, cathode and organic function layer, and organic function layer includes hole injection layer, hole transmission layer, electronic blocking
At least one layer in layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer；At least containing in the luminescent layer
A kind of organic coordination compound containing metal described above.The organic luminescent device of the present invention is that flat panel shows, is flat luminous
Body, illumination face illuminating OLED illuminator, flexible illuminator, duplicator, printer, LCD backlight lamp or dosing machine class light source,
The suitable use such as display board, mark.
The present invention is not particularly limited the raw material employed in following embodiment, can be for commercial product or using this
Preparation method known to field technology personnel is prepared.
Embodiment 1：The preparation of compound 1
The preparation of intermediate A 1
Under nitrogen protection, compound a 1 (7.15g, 30.7mmol) and compound b1 (3.77g, 30.7mmol) are added
In 100mL four-hole boiling flasks, and add four triphenyl phosphorus palladium Pd (PPh3)4(1.8g, 1.53mmol) and K2CO3(8.48g,
It 61.4mmol) is dissolved in toluene (150ml) and water (30ml).Then it holds the mixture at 100 DEG C overnight.It completes to react
Afterwards, mixture is cooled to room temperature, and with brine and water washing, is dried to obtain intermediate A 1 (6.28g, yield 88%).
The preparation of intermediate B 1
In 1L there-necked flasks, be added hydrated iridium trichloride (14.11g, 40mmol) and intermediate A 1 (39.49g,
170mmol), 300mL2- ethoxy ethanols and 100mL water is then added, mixture is refluxed overnight in a nitrogen atmosphere.Reaction
After, it is cooled to room temperature, precipitation is filtered and is washed with methanol, intermediate B 1 (24.85g, yield 90%) is dried to obtain.
Mass spectrum m/z：1378.24 (calculated value：1378.23).Theoretical elemental content (%) C64H44Cl2Ir2N8：C,55.69；
H,3.21；Cl,5.14；Ir,27.85；N, 8.12 actual measurement constituent contents (%)：C,55.69；H,3.20；Cl,5.14；Ir,
27.86；N,8.12.The above results confirm that it is target product to obtain product.
The preparation of compound 1
The hexane solution (100mL) of bromobenzene-c1 (3.1g, 20mmol) is added in 100mL four-hole boiling flasks, 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 dichloromethane, concentration
Column chromatography obtains compound 1 (5.15g, 30%).
Mass spectrum m/z：859.32 (calculated values：859.31).Theoretical elemental content (%) C45H42IrN6：C,62.91；H,
4.93；Ir,22.37；N, 9.78 actual measurement constituent contents (%)：C,62.91；H,4.92；Ir,22.38；N,9.78.The above results
Confirm that it is target product to obtain product.
Embodiment 2：The preparation of compound 4
Change the b1 in embodiment 1 into equimolar b4, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 4 (4.99g, 29%).
Mass spectrum m/z：861.31 (calculated values：861.30).Theoretical elemental content (%) C43H40IrN8：C,59.98；H,
4.68；Ir,22.32；N, 13.01 actual measurement constituent contents (%)：C,59.99；H,4.67；Ir,22.33；N,13.00.Above-mentioned knot
Fruit confirms that it is target product to obtain product.
Embodiment 3：The preparation of compound 6
Change the b1 in embodiment 1 into equimolar b6, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 6 (5.00g, 29%).
Mass spectrum m/z：863.30 (calculated values：863.29).Theoretical elemental content (%) C41H38IrN10：C,57.06；H,
4.44；Ir,22.27；N, 16.23 actual measurement constituent contents (%)：C,57.06；H,4.43；Ir,22.28；N,16.23.Above-mentioned knot
Fruit confirms that it is target product to obtain product.
Embodiment 4：The preparation of compound 9
Change the b1 in embodiment 1 into equimolar b9, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 9 (5.03g, 30%).
Mass spectrum m/z：839.28 (calculated values：839.27).Theoretical elemental content (%) C41H38IrN6O2：C,58.69；H,
4.57；Ir,22.91；N,10.02；O, 3.81 actual measurement constituent contents (%)：C,58.69；H,4.56；Ir,22.91；N,10.03；
O,3.81.The above results confirm that it is target product to obtain product.
Embodiment 5：The preparation of compound 18
Change the b1 in embodiment 1 into equimolar b18, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 18 (5.76g, 30%).
Mass spectrum m/z：959.35 (calculated values：959.34).Theoretical elemental content (%) C53H46IrN6：C,66.37；H,
4.83；Ir,20.04；N, 8.76 actual measurement constituent contents (%)：C,66.38；H,4.82；Ir,20.05；N,8.75.The above results
Confirm that it is target product to obtain product.
Embodiment 6：The preparation of compound 29
Change the bromobenzene-c1 in embodiment 1 into equimolar c29, other steps are identical as the synthesis of embodiment 1, obtain
To target product compound 29 (5.12g, 31%).
Mass spectrum m/z：825.34 (calculated values：825.33).Theoretical elemental content (%) C42H44IrN6：C,61.14；H,
5.38；Ir,23.30；N, 10.19 actual measurement constituent contents (%)：C,61.15；H,5.38；Ir,23.30；N,10.18.Above-mentioned knot
Fruit confirms that it is target product to obtain product.
Embodiment 7：The preparation of compound 32
Change the b1 in embodiment 1 into equimolar b4, bromobenzene-c1 changes equimolar c32 into, other steps with implementation
The synthesis of example 1 is identical, obtains target product compound 32 (5.32g, 28%).
Mass spectrum m/z：950.36 (calculated values：950.35).Theoretical elemental content (%) C51H47IrN7：C,64.47；H,
4.99；Ir,20.23；N, 10.32 actual measurement constituent contents (%)：C,64.47；H,4.98；Ir,20.24；N,10.32.Above-mentioned knot
Fruit confirms that it is target product to obtain product.
Embodiment 8：The preparation of compound 34
Change the bromobenzene-c1 in embodiment 1 into equimolar c34, other steps are identical as the synthesis of embodiment 1, obtain
To target product compound 34 (5.45g, 30%).
Mass spectrum m/z：909.34 (calculated values：909.33).Theoretical elemental content (%) C49H44IrN6：C,64.74；H,
4.88；Ir,21.14；N, 9.24 actual measurement constituent contents (%)：C,64.75；H,4.88；Ir,21.14；N,9.23.The above results
Confirm that it is target product to obtain product.
Embodiment 9：The preparation of compound 35
Change the bromobenzene-c1 in embodiment 1 into equimolar c35, other steps are identical as the synthesis of embodiment 1, obtain
To target product compound 35 (5.50g, 29%).
Mass spectrum m/z：948.35 (calculated values：948.34).Theoretical elemental content (%) C51H45IrN7：C,64.60；H,
4.78；Ir,20.27；N, 10.34 actual measurement constituent contents (%)：C,64.60；H,4.77；Ir,20.28；N,10.34.Above-mentioned knot
Fruit confirms that it is target product to obtain product.
Embodiment 10：The preparation of compound 41
By the N in embodiment 1, N '-diisopropylcarbodiimide changes equimolar N into, N '-diethyl carbodiimides,
His step is identical as the synthesis of embodiment 1, obtains target product compound 41 (4.65g, 28%).
Mass spectrum m/z：831.29 (calculated values：831.28).Theoretical elemental content (%) C43H38IrN6：C,62.15；H,
4.61；Ir,23.13；N, 10.11 actual measurement constituent contents (%)：C,62.15；H,4.60；Ir,23.13；N,10.12.Above-mentioned knot
Fruit confirms that it is target product to obtain product.
Embodiment 11：The preparation of compound 45
By the N in embodiment 1, N '-diisopropylcarbodiimide changes equimolar N into, N '-dicyclohexylcarbodiimides,
Other steps are identical as the synthesis of embodiment 1, obtain target product compound 45 (5.07g, 27%).
Mass spectrum m/z：939.38 (calculated values：939.37).Theoretical elemental content (%) C51H50IrN6：C,65.22；H,
5.37；Ir,20.47；N, 8.95 actual measurement constituent contents (%)：C,65.23；H,5.37；Ir,20.46；N,8.95.The above results
Confirm that it is target product to obtain product.
Embodiment 12：The preparation of compound 49
Change the a1 in embodiment 1 into equimolar a49, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 49 (5.15g, 30%).
Mass spectrum m/z：859.32 (calculated values：859.31).Theoretical elemental content (%) C45H42IrN6：C,62.91；H,
4.93；Ir,22.37；N, 9.78 actual measurement constituent contents (%)：C,62.91；H,4.92；Ir,22.38；N,9.78.The above results
Confirm that it is target product to obtain product.
Embodiment 13：The preparation of compound 80
Change the a1 in embodiment 1 into equimolar a49, b1 changes equimolar b4 into, and bromobenzene-c1 changes into equimolar
C32, other steps are identical as the synthesis of embodiment 1, obtain target product compound 80 (5.32g, 28%).
Mass spectrum m/z：950.36 (calculated values：950.35).Theoretical elemental content (%) C51H47IrN7：C,64.47；H,
4.99；Ir,20.23；N, 10.32 actual measurement constituent contents (%)：C,64.47；H,4.98；Ir,20.24；N,10.32.Above-mentioned knot
Fruit confirms that it is target product to obtain product.
Embodiment 14：The preparation of compound 89
Changing the a1 in embodiment 1 into equimolar a49, N, N '-diisopropylcarbodiimide changes equimolar N, N '-into
Diethyl carbodiimide, other steps are identical as the synthesis of embodiment 1, obtain target product compound 89 (4.65g,
28%).
Mass spectrum m/z：831.29 (calculated values：831.28).Theoretical elemental content (%) C43H38IrN6：C,62.15；H,
4.61；Ir,23.13；N, 10.11 actual measurement constituent contents (%)：C,62.15；H,4.60；Ir,23.13；N,10.12.Above-mentioned knot
Fruit confirms that it is target product to obtain product.
Embodiment 15：The preparation of compound 97
Change the a1 in embodiment 1 into equimolar a97, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound 97 (4.98g, 29%).
Mass spectrum m/z：859.32 (calculated values：859.31).Theoretical elemental content (%) C45H42IrN6：C,62.91；H,
4.93；Ir,22.37；N, 9.78 actual measurement constituent contents (%)：C,62.91；H,4.92；Ir,22.38；N,9.78.The above results
Confirm that it is target product to obtain product.
Compare Application Example 1
Ito glass substrate is placed in distilled water and is cleaned 2 times, ultrasonic washing 15 minutes is 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 being already prepared to, vapor deposition hole passes
Defeated layer NPB/30nm, vapor deposition main body CBP：Adulterate Ir (piq)2(acac) 5% mixing/30nm and then vapor deposition electron transfer layer
TPBi/30nm, cathode LiF/0.5nm, Al/200nm.
[Application Example 1-15]
The Ir (piq) in Application Example 1 will be compared2(acac) change into shown compound 1 in Application Example 1-15,
4、6、9、18、29、32、34、35、41、45、49、80、89、97。
Table 1 is compound prepared by the embodiment of the present invention and compares the characteristics of luminescence test of the luminescent device of substance preparation
As a result.
The characteristics of luminescence of [table 1] luminescent device is tested
The above result shows that a kind of organic coordination compound containing metal of the invention is applied in organic luminescent device, especially
It is to show the low advantage of high-luminous-efficiency, driving voltage as luminescent layer guest materials, is organic light emission material of good performance
Material.
Obviously, the explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should refer to
Go out, it, 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, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (7)
1. a kind of organic coordination compound containing metal, which is characterized in that shown in structural formula such as formula (I)：
Wherein, R1、R2Independently selected from substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6~C25 aryl, take
One kind in generation or unsubstituted C3~C18 heteroaryls；
R3Selected from substituted or unsubstituted C1~C10 alkyl, the silylation of substituted or unsubstituted C1~C10, substitution or unsubstituted
C6~C25 aryl, the heteroaryl of substituted or unsubstituted C3~C18, one in the amido of substituted or unsubstituted C2~C20
Kind；
R4-R7Independently selected from hydrogen, cyano, halogen atom, substituted or unsubstituted C1~C10 alkyl, substituted or unsubstituted C6
One kind in~C25 aryl, substituted or unsubstituted C3~C18 heteroaryls；
M is selected from Ir.
RAOne kind in following group：
2. a kind of organic coordination compound containing metal according to claim 1, which is characterized in that R1、R2Independently selected from first
One kind in base, ethyl, propyl, isopropyl, butyl, isobutyl group, tertiary butyl, cyclohexyl, phenyl, xenyl, naphthalene.
3. a kind of organic coordination compound containing metal according to claim 1, which is characterized in that R3Selected from methyl, ethyl, different
In propyl, tertiary butyl, cyclohexyl, trimethylsilyl, phenyl, xenyl, naphthalene, amido, fluorenyl, carbazyl, acridinyl
It is a kind of.
4. a kind of organic coordination compound containing metal according to claim 1, which is characterized in that R4-R7Independently selected from hydrogen,
Cyano, halogen atom or substituted or unsubstituted following group：C1~C6 alkyl, phenyl, naphthalene, anthryl, phenanthryl, pyrenyl, fluorenes
Base, two fluorenyl of spiral shell, carbazyl, pyridyl group, pyrimidine radicals, triazine radical, phenothiazinyl, phenoxazine groups, acridinyl, dibenzothiophenes
One kind in base, dibenzofuran group, benzothienyl, benzofuranyl, quinolyl or isoquinolyl.
5. a kind of organic coordination compound containing metal according to claim 1, which is characterized in that organic containing metal matches
Close any one of object in structure as follows：
6. 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 matching containing a kind of organic containing metal of Claims 1 to 5 any one of them in the organic function layer
Close object.
7. wanting a kind of organic luminescent device described in 6 according to right, which is characterized in that the organic function layer includes hole injection
Layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer, in luminescent layer at least
Contain a kind of organic coordination compound containing metal of Claims 1 to 5 any one of them.
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Cited By (2)
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|---|---|---|---|---|
| US20220310943A1 (en) * | 2021-03-04 | 2022-09-29 | Samsung Display Co., Ltd. | Organometallic compound, light-emitting device including the same, and electronic apparatus including the light-emitting device |
| US11999886B2 (en) | 2019-09-26 | 2024-06-04 | Universal Display Corporation | Organic electroluminescent materials and devices |
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2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11999886B2 (en) | 2019-09-26 | 2024-06-04 | Universal Display Corporation | Organic electroluminescent materials and devices |
| US20220310943A1 (en) * | 2021-03-04 | 2022-09-29 | Samsung Display Co., Ltd. | Organometallic compound, light-emitting device including the same, and electronic apparatus including the light-emitting device |
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