CN108912175A - A kind of metal iridium complex and its organic luminescent device - Google Patents
A kind of metal iridium complex and its organic luminescent device Download PDFInfo
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- CN108912175A CN108912175A CN201810576303.6A CN201810576303A CN108912175A CN 108912175 A CN108912175 A CN 108912175A CN 201810576303 A CN201810576303 A CN 201810576303A CN 108912175 A CN108912175 A CN 108912175A
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
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- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
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- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Abstract
The invention discloses a kind of metal iridium complex and its organic luminescent devices, are related to organic optoelectronic materials technology.Guanidine group with class Cabbeen structure is introduced into metal complex molecule by we as assistant ligand, has constructed a kind of four-membered ring coordination structure, has obtained a series of green phosphorescent complex material systems with completely new molecular structure and photoelectric properties.Due to its iridium atom with the more stable positive trivalent in center, make complex that there is better chemical stability and thermal stability, and unnecessary vibrational energy loss can be reduced, to drop low molecular nonradiative transition to improve the luminous efficiency of complex.Its diffraction is prepared into device, especially as dopant material, device shows the advantage that driving voltage is low, luminous efficiency is high and excitation purity is preferable, is better than existing common OLED device.
Description
Technical field
The present invention relates to organic photoelectrical material technical field more particularly to a kind of metal iridium complexes and its organic illuminator
Part.
Background technique
Organic electroluminescent LED (Organic Light Emitting Diode, OLED) is to utilize electrons and holes
The recombination luminescence in organic film and the luminescent device prepared, have the following advantages that：(1) from main light emission, backlight is not needed；
(2) brightness is high, there is high contrast, pure in colour, the problem of almost without visible angle；(3) ultra-thin, by very thin organic
Material coating and basis material are constituted, small in size to be suitable for portable product；(4) power consumption is very small, environmental protection and energy saving；(5) it rings
It answers speed fast, is the one thousandth of LCD；(6) use temperature range is wide, remains to normally show at -40 DEG C.
General organic luminescent device (OLED) is the organic matter layer structure by being inserted between cathode, anode and cathode and anode
At, the composition of device is transparent ITO anode, hole injection layer (TIL), hole transmission layer (HTL), luminescent layer (EL), hole
The cathodes such as barrier layer (HBL), electron transfer layer (ETL), electron injecting layer (EIL), LiAl are formed.
Emitting layer material is divided into fluorescent material and phosphor material, and the forming method of luminescent layer is adulterated in fluorescent host material
The method of method and fluorescent host material doping fluorescent (organic matter comprising nitrogen) dopant of phosphor material (organic metal).Its
In, heavy metal complex causes in the application study of organic electroluminescent LED greatly due to its efficient luminescent properties
Attention.And these metal complexs for being used as organic electroluminescent LED are mostly 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, efficiently
It is since the configuration of extra-nuclear electron of metal complex has caused by strong SO coupling that the phosphorescence of rate, which shines,.
Currently, the research of electroluminescent organic material is carried out in academia and industry extensively, a large amount of function admirables
Electroluminescent organic material be developed successively, but the technological industrialization process still faces many critical issues how
The luminescent material for designing the better metal iridium complex of new performance is adjusted, and is always that those skilled in the art are urgently to be resolved
The problem of.
Summary of the invention
The object of the present invention is to provide a kind of metal iridium complex and its organic luminescent devices.Metal iridium provided by the invention
Thermal analysis can be high, which is used to use and manufactured organic luminescent device in luminescent layer, table by good film-forming property
Reveal the advantage that driving voltage is low, luminous efficiency is high and excitation purity is preferable, is the luminous organic material of function admirable.
The present invention provides a kind of metal iridium complexes, and general formula of molecular structure is as shown in I：
Wherein, X1、X2Independently selected from nitrogen-atoms, oxygen atom, sulphur atom or phosphorus atoms；
Y is oxygen atom, sulphur atom or NRa, the RaSelected from substituted or unsubstituted C1~C10Alkyl, replace or do not take
The C in generation1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl in
One kind；
R1Selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C2~C10Alkenyl, replace or not
Substituted C2~C10Alkynyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C1~C10Boryl,
Substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl, substituted or unsubstituted C2~C50
One of amino；
R2~R3Independently selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Alcoxyl
Base, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50One of heteroaryl；
R4~R9Independently selected from hydrogen atom, halogen atom, substituted or unsubstituted C1~C10Alkyl, replace or do not take
The C in generation1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl, take
Generation or unsubstituted C2~C50One of amino or the R4、R5Connection cyclization or the R6~R9Middle adjacent pairs connect
It is looped.
Preferably, a kind of metal iridium complex, X in general formula of molecular structure1And X2For nitrogen-atoms.
Preferably, a kind of metal iridium complex, general formula of molecular structure is as shown in II：
Wherein, Z is oxygen atom, sulphur atom, NRaOr CRbRc, the Ra~RcIndependently selected from substituted or unsubstituted C1~
C10Alkyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted
C3~C50One of heteroaryl；R10Selected from hydrogen atom, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted
C1~C10Alkoxy, substituted or unsubstituted C1~C10Boryl, substituted or unsubstituted C6~C50Aryl, replace
Or unsubstituted C3~C50Heteroaryl, substituted or unsubstituted C2~C50One of amino.
Preferably, a kind of metal iridium complex, Y is oxygen atom or sulphur atom in general formula of molecular structure.
Preferably, a kind of metal iridium complex, R in general formula of molecular structure1Selected from methyl, ethyl, isopropyl,
Tert-butyl, cyclohexyl, trimethylsilyl, phenyl, xenyl, naphthalene, amino, fluorenyl, carbazyl, acridinyl, pyridyl group, pyrrole
Piperazine base or triazine radical.
Preferably, a kind of metal iridium complex, R in general formula of molecular structure2~R3Independently selected from methyl, second
Base, isopropyl, tert-butyl, cyclohexyl, phenyl, xenyl, naphthalene, pyridyl group, pyrazinyl or triazine radical.
Preferably, a kind of metal iridium complex, the structure on the right side of metal iridium are with one of flowering structure：
Further preferably, any one of a kind of metal iridium complex in chemical structure as follows：
The present invention also provides a kind of organic luminescent device, including cathode, anode and it is placed in the cathode and the anode
Between one or more organic compound layers, the organic compound layer contains a kind of described in any item metal iridiums cooperations
Object.
Preferably, organic compound layer includes luminescent layer, contains a kind of described in any item metal iridium cooperations in luminescent layer
Object.
Beneficial effects of the present invention：
The present invention provides a kind of metal iridium complexes, have the following effects that：
On the one hand, the guanidine group with class Cabbeen structure is introduced metal complex molecule as assistant ligand by us
In, a kind of four-membered ring coordination structure, i.e. Ir-N-C-N ring have been constructed, has replaced in traditional complex and uses pentanedione (acac)
The hexa-atomic ring configuration that the assistant ligands such as derivative and central metal atom are formed, to obtain a series of with completely new molecule knot
The green phosphorescent complex material system of structure and photoelectric properties.The electron rich coordination structure of this dinitrogen can it is preferably stable in
The iridium atom of the positive trivalent of the heart, to obtain higher chemical stability and thermal stability.
On the other hand, since four-membered ring is more more rigid than six-membered ring structure and close, the connection with center iridium atom is more
Closely, unnecessary vibrational energy loss can be reduced, so that low molecular nonradiative transition is dropped, it in this way can be in synthesis green
It reduces the negative effect of energy gap rule bring when luminescent material to the greatest extent, and the luminous efficiency of complex is greatly improved, have
Effect reduces burying in oblivion for triplet excitons.
Metal iridium complex is prepared into device, especially as dopant material, it is low, luminous that device shows driving voltage
High-efficient and preferable excitation purity advantage is better than existing common OLED device.What is shown in OLED luminescent device is good
Application effect, this point show it with good industrialization prospect.
Specific embodiment：
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, art technology
Personnel's every other embodiment obtained without making creative work, belongs to protection scope of the present invention.
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.
Amino of the present invention refers to be made of a nitrogen-atoms and two hydrogen atoms, chemical formula-NH2, can be alkane
Amino or aryl amine, example may include-N (CH3)2、-N(CH2CH3)2With such as flowering structure, but not limited to this
Aryl that substituted alkyl of the present invention, substituted alkoxy, substituted amino replace, substituted heteroaryl,
Substituted amino, the substituent group is independent to be selected from methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthalene, anthryl, phenanthryl, benzene
And phenanthryl, base, pyrenyl, benzyl, methoxyl group, methyl mercapto, phenoxy group, thiophenyl, fluorenyl, 9,9- dimethyl fluorenyl, hexichol
Amido, dimethylamino, carbazyl, 9- phenyl carbazole base, furyl, thienyl, cyano, halogen, deuterium base, triphenyl silicon substrate, three
Methylsilyl, trifluoromethyl, phenothiazinyl, phenoxazine group, acridinyl, piperidyl, pyridyl group, pyrazinyl, triazine radical, pyrimidine
Base, xenyl, terphenyl, nitro etc., but not limited to this.
Connection cyclization of the present invention refers to that two groups are connected to each other by chemical bond.As follows：
However, in addition, above-mentioned statement is also intended to is considered referring to, in the case where wherein one of two groups are hydrogen, hydrogen
Atom position bonding, thus cyclic.As follows：
In addition, the ring being connected to further includes dibenzofuran group, dibenzothiophene, phenanthryl, pyrenyl, but not limited to this.
The present invention provides a kind of metal iridium complexes, and general formula of molecular structure is as shown in I：
Wherein, X1、X2Independently selected from nitrogen-atoms, oxygen atom, sulphur atom or phosphorus atoms；
Y is oxygen atom, sulphur atom or NRa, the RaSelected from substituted or unsubstituted C1~C10Alkyl, replace or do not take
The C in generation1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl in
One kind；
R1Selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C2~C10Alkenyl, replace or not
Substituted C2~C10Alkynyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C1~C10Boryl,
Substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl, substituted or unsubstituted C2~C50
One of amino；
R2~R3Independently selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Alcoxyl
Base, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50One of heteroaryl；
R4~R9Independently selected from hydrogen atom, halogen atom, substituted or unsubstituted C1~C10Alkyl, replace or do not take
The C in generation1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl, take
Generation or unsubstituted C2~C50One of amino or the R4、R5Connection cyclization or the R6~R9Middle adjacent pairs connect
It is looped.
Preferably, a kind of metal iridium complex, X in general formula of molecular structure1And X2For nitrogen-atoms.
Preferably, a kind of metal iridium complex, general formula of molecular structure is as shown in II：
Wherein, Z is oxygen atom, sulphur atom, NRaOr CRbRc, the Ra~RcIndependently selected from substituted or unsubstituted C1~
C10Alkyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted
C3~C50One of heteroaryl；R10Selected from hydrogen atom, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted
C1~C10Alkoxy, substituted or unsubstituted C1~C10Boryl, substituted or unsubstituted C6~C50Aryl, replace
Or unsubstituted C3~C50Heteroaryl, substituted or unsubstituted C2~C50One of amino.
Preferably, a kind of metal iridium complex, Y is oxygen atom or sulphur atom in general formula of molecular structure.
Preferably, a kind of metal iridium complex, R in general formula of molecular structure2~R3Independently selected from methyl, second
Base, isopropyl, tert-butyl, cyclohexyl, phenyl, xenyl, naphthalene, pyridyl group, pyrazinyl or triazine radical.
Preferably, a kind of metal iridium complex, R in general formula of molecular structure4Selected from methyl, ethyl, isopropyl,
Tert-butyl, cyclohexyl, trimethylsilyl, phenyl, xenyl, naphthalene, amino, fluorenyl, carbazyl, acridinyl, pyridyl group, pyrrole
Piperazine base or triazine radical.
Preferably, a kind of metal iridium complex, the structure on the right side of metal iridium are with one of flowering structure：
Further preferably, a kind of metal iridium complex, any one in chemical structure as follows：
A kind of metal iridium complex of the invention, preparation route are as follows：
According to the present invention, intermediate A is prepared according to method as follows：
Bromo-derivative a reacts to obtain boronic acid compounds b with triisopropyl borate ester, is coupled instead with compound c by Suzuki
Compound d should be obtained, later under nitrogen protection, compound d reacts in cellosolvo solvent with hydrated iridium trichloride
Obtain target product intermediate A.
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
B.Intermediate A reacts to obtain target product compound I with intermediate B.
The present invention limitation not special to above-mentioned reaction be using popular response well-known to those skilled in the art
Can, the preparation method is easy to operate, is readily produced.
The present invention also provides a kind of organic luminescent device, including cathode, anode and it is placed in the cathode and the anode
Between one or more organic compound layers, organic compound layer include hole injection layer, hole transmission layer, electronic blocking
At least one layer of layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer；At least one in the organic compound layer
Layer includes a kind of metal iridium complex of the present invention.
Preferably, a kind of metal iridium complex can be used as the dopant material in organic luminescent device.The device of use
Part structure is preferably specially：NPB is used as hole mobile material, and CBP is used as material of main part, and a kind of metal iridium complex is used
Make dopant material, TPBi is used as electron transport material, to manufacture the organic luminescent device of construction same as below：ITO/NPB/
CBP：A kind of metal iridium complex (the 5%)/TPBi/LiF/Al.It is aobvious that the organic electroluminescence device can be used for plate
Show the application fields such as device, lighting source, direction board, signal lamp.
The synthesis of [embodiment 1] compound TM1
The synthesis of intermediate A 1
Under the protection of nitrogen, take compound a 1 (24.7g, 0.1mol), after suitable anhydrous THF dissolution is added, cooling
To -78 DEG C, it is added dropwise n-BuLi (150ml, 0.22mol, 1.6M), insulation reaction 0.5 hour, three isopropyl ester of fast drop boric acid
(20.7g, 0.11mol) is slowly warming up to room temperature, reacts 30min.After completion of the reaction, reaction solution is to entering in diluted hydrochloric acid aqueous solution
In, there is solid matter that filtering is precipitated, crude product chromatographs to obtain compound b1 via column.
By compound b1 (21.2g, 0.1mol), 2- bromine Evil azoles (14.8g, 0.1mol), potassium carbonate (69g, 0.5mol),
300mL water, 1L toluene are in 2L there-necked flask, nitrogen protection, stirring at normal temperature, and system is white opacity, and four triphens are added after 20min
Base phosphine palladium (1.1g, 1%), is heated to reflux 12 hours, and system generates a large amount of solids, and suction filtration obtains solid product compound d1
(18.8g, yield 80%).
In 1L there-necked flask, hydrated iridium trichloride (14.1g, 40mmol) and compound d1 (40.0g, 170mmol) is added,
Then 300mL cellosolvo and 100mL water is added, mixture is refluxed overnight in a nitrogen atmosphere.After reaction,
It is cooled to room temperature, precipitating is filtered and is washed with methanol, intermediate A 1 (50.0g, yield 90%) is dried to obtain.Mass spectrum m/z：
1392.19 (calculated value：1392.26).Theoretical elemental content (%) C60H32Cl2Ir2N4O8：C,51.76；H,2.32；Cl,5.09；
Ir,27.61；N,4.02；O, 9.19 actual measurements constituent content (%)：C,51.76；H,2.33；Cl,5.08；Ir,27.63；N,
4.02；O,9.17.The above results confirm that obtaining product is target product.
The synthesis of compound TM1
The hexane solution (100mL) of bromobenzene (3.1g, 20mmol) is added in 100mL four-hole boiling flask, is cooled to -80
DEG C, the hexane solution (8mL) of the n-BuLi of 2.5M is added dropwise under nitrogen atmosphere, after stirring 1.5 hours, into mixed liquor
N is added dropwise, N '-diisopropylcarbodiimide (2.5g, 20mmol) after being added dropwise, continues stirring 2 hours, obtains faint yellow molten
This solution is added dropwise in tetrahydrofuran (100mL) solution of intermediate A 1 (13.9,10mmol) by liquid, after being added dropwise, heating
To 60 DEG C, stir 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 use
Methylene chloride dissolution, evaporating column chromatography, obtains compound TM1 (4.7g, 30%).Mass spectrum m/z：864.89 (calculated values：
864.99).Theoretical elemental content (%) C43H36IrN4O4：C,59.71；H,4.19；Ir,22.22；N,6.48；O, 7.40 actual measurements
Constituent content (%)：C,59.71；H,4.19；Ir,22.22；N,6.46；O,7.42.The above results confirm that obtaining product is target
Product.
The synthesis of [embodiment 2] compound TM9
Change the compound a 1 in embodiment 1 into equimolar 1- bromo- 9,9- dimethyl fluorene, 2- bromine Evil azoles changes equimolar into
The bromo- 4- trifluoromethyl Evil azoles of 2-, other steps are identical as the synthesis of embodiment 1, obtain target product compound TM9.Matter
Compose m/z：1053.09 (calculated value：1053.14).Theoretical elemental content (%) C51H46F6IrN4O2：C,58.16；H,4.40；F,
10.82；Ir,18.25；N,5.32；O, 3.04 actual measurements constituent content (%)：C,58.16；H,4.41；F,10.82；Ir,18.24；
N,5.33；O,3.03.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 3] compound TM18
Change the compound a 1 in embodiment 1 into equimolar 1- bromo- 9- phenyl -9H- carbazole, 2- bromine Evil azoles, which changes into, etc. rubs
Your bromo- 4,5- dimethyl Evil azoles of 2-, other steps are identical as the synthesis of embodiment 1, obtain target product compound TM18.
Mass spectrum m/z：1071.36 (calculated value：1071.32).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,7.85；O,2.97.On
Stating result confirms that obtaining product is target product.
The synthesis of [embodiment 4] compound 39
Change the compound a 1 in embodiment 1 into equimolar 1- bromo- 9,9- dimethyl fluorene, bromobenzene changes into equimolar
The bromo- N- phenylaniline of N-, other steps are identical as the synthesis of embodiment 1, obtain target product compound TM39.Mass spectrum m/z：
1008.19 (calculated value：1008.26).Theoretical elemental content (%) C55H53IrN5O2：C,65.52；H,5.30；Ir,19.06；N,
6.95；O, 3.17 actual measurements constituent content (%)：C,65.53；H,5.31；Ir,19.06；N,6.95；O,3.15.The above results card
The real product that obtains is target product.
The synthesis of [embodiment 5] compound TM52
Change the compound a 1 in embodiment 1 into equimolar 1- bromo- 9- methyl -9H- carbazole, 2- bromine Evil azoles, which changes into, etc. rubs
Your 2- bromobenzene and Evil azoles, other steps are identical as the synthesis of embodiment 1, obtain target product compound TM52.Mass spectrum m/
z：1115.45 (calculated value：1115.33).Theoretical elemental content (%) C63H50IrN6O2：C,67.84；H,4.52；Ir,17.23；
N,7.54；O, 2.87 actual measurements constituent content (%)：C,67.84；H,4.54；Ir,17.23；N,7.53；O,2.86.The above results
Confirm that obtaining product is target product.
The synthesis of [embodiment 6] compound T1
Change the 2- bromine Evil azoles in embodiment 1 into equimolar 2- bromo thiazole, other steps with the synthesis phase of embodiment 1
Together, target product compound T1 is obtained.Mass spectrum m/z：897.19 (calculated values：897.12).Theoretical elemental content (%)
C43H36IrN4O2S2：C,57.57；H,4.40；Ir,21.43；N,6.25；O,3.57；S, 7.15 actual measurements constituent content (%)：C,
57.56；H,4.41；Ir,21.44；N,6.25；O,3.56；S,7.15.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 7] compound T9
Change the compound a 1 in embodiment 1 into equimolar 1- bromo- 9,9- dimethyl fluorene, 2- bromine Evil azoles changes equimolar into
The bromo- 4- trifluoromethyl thiazole of 2-, other steps are identical as the synthesis of embodiment 1, obtain target product compound T9.Mass spectrum
m/z：1085.25 (calculated value：1085.28).Theoretical elemental content (%) C51H46F6IrN4S2：C,56.44；H,4.27；F,
10.50；Ir,17.71；N,5.16；S, 5.91 actual measurements constituent content (%)：C,56.44；H,4.25；F,10.52；Ir,17.71；
N,5.16；S,5.91.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 8] compound T18
Change the compound a 1 in embodiment 1 into equimolar 1- bromo- 9- phenyl -9H- carbazole, 2- bromine Evil azoles, which changes into, etc. rubs
Your bromo- 4,5- dimethylthiazole of 2-, other steps are identical as the synthesis of embodiment 1, obtain target product compound T18.
Mass spectrum m/z：1103.36 (calculated value：1103.45).Theoretical elemental content (%) C59H54IrN6S2：C,64.22；H,4.93；Ir,
17.42；N,7.62；S, 5.81 actual measurements constituent content (%)：C,64.21；H,4.93；Ir,17.43；N,7.62；S,5.81.On
Stating result confirms that obtaining product is target product.
The synthesis of [embodiment 9] compound T39
Change the compound a 1 in embodiment 1 into equimolar 1- bromo- 9,9- dimethyl fluorene, 2- bromine Evil azoles changes equimolar into
2- bromo thiazole, bromobenzene changes the bromo- N- phenylaniline of equimolar N- into, other steps are identical as the synthesis of embodiment 1, obtain
To target product compound T39.Mass spectrum m/z：1040.40 (calculated value：1040.39).Theoretical elemental content (%)
C55H53IrN5S2：C,63.49；H,5.13；Ir,18.48；N,6.73；S, 6.16 actual measurements constituent content (%)：C,63.48；H,
5.14；Ir,18.48；N,6.74；S,6.16.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 10] compound T52
Change the compound a 1 in embodiment 1 into equimolar 1- bromo- 9- methyl -9H- carbazole, 2- bromine Evil azoles, which changes into, etc. rubs
Your 2- bromo benzothiazole, other steps are identical as the synthesis of embodiment 1, obtain target product compound T52.Mass spectrum m/z：
1147.45 (calculated value：1147.46).Theoretical elemental content (%) C63H50IrN6S2：C,65.94；H,4.39；Ir,16.75；N,
7.32；S, 5.59 actual measurements constituent content (%)：C,65.94；H,4.39；Ir,16.75；N,7.34；S,5.57.The above results card
The real product that obtains is target product.
The synthesis of [embodiment 11] compound T61
The 2- bromine Evil azoles in embodiment 1 is changed into equimolar 2- bromo thiazole, N, N '-diisopropylcarbodiimide to change into
Mole N, N '-di-t-butyl carbodiimide, other steps are identical as the synthesis of embodiment 1, obtain target product compound
T61.Mass spectrum m/z：1025.19 (calculated value：1025.25).Theoretical elemental content (%) C53H54IrN4O2S2：C,62.09；H,
4.33；Ir,18.75；N,5.46；O,3.12；S, 6.25 actual measurements constituent content (%)：C,62.09；H,4.33；Ir,18.75；N,
5.45；O,3.13；S,6.25.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 12] compound T67
The 2- bromine Evil azoles in embodiment 1 is changed into equimolar 2- bromo thiazole, N, N '-diisopropylcarbodiimide to change into
Mole N, N '-dicyclohexylcarbodiimide, other steps are identical as the synthesis of embodiment 1, obtain target product compound
T67.Mass spectrum m/z：1077.19 (calculated value：1077.28).Theoretical elemental content (%) C57H48IrN4O2S2：C,63.54；H,
4.49；Ir,17.82；N,5.20；O,2.97；S, 5.95 actual measurements constituent content (%)：C,63.54；H,4.47；Ir,17.84；N,
5.20；O,2.97；S,5.95.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 13] compound T76
The 2- bromine Evil azoles in embodiment 1 is changed into equimolar 2- bromo thiazole, N, N '-diisopropylcarbodiimide to change into
Mole 1- tert-butyl -3- ethyl carbodiimide, other steps are identical as the synthesis of embodiment 1, obtain target product chemical combination
Object T76.Mass spectrum m/z：997.19 (calculated values：997.22).Theoretical elemental content (%) C51H40IrN4O2S2：C,61.42；H,
4.04；Ir,19.27；N,5.62；O,3.21；S, 6.43 actual measurements constituent content (%)：C,61.44；H,4.04；Ir,19.25；N,
5.62；O,3.21；S,6.43.The above results confirm that obtaining product is target product.
[comparison Application Example]
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and exposure 30 minutes under ultraviolet light,
Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.It is deposited one layer of 70nm's first
NPB is as hole transmission layer, evaporation rate 0.1nm/s, followed by the vapor deposition of luminescent layer, mixing vapor deposition CBP/Ir (PPy)3,
Doping concentration is 5wt%, evaporation rate 0.005nm/s, evaporation thickness 30nm, and the TPBi of 50nm is then deposited as electronics
Transport layer, evaporation rate 0.01nm/s, on the electron transport layer successively vacuum evaporation LiF and Al as cathode, with a thickness of
200nm。
[Application Example]
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and exposure 30 minutes under ultraviolet light,
Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.It is deposited one layer of 70nm's first
One kind described in CBP/ is deposited as hole transmission layer, evaporation rate 0.1nm/s, followed by the vapor deposition of luminescent layer, mixing in NPB
Metal iridium complex, doping concentration 5wt%, evaporation rate 0.005nm/s, the TPBi that 50nm is then deposited are passed as electronics
Defeated layer, evaporation rate 0.01nm/s, on the electron transport layer successively vacuum evaporation LiF and Al as cathode, with a thickness of
200nm。
The electron luminescence characteristic of the organic luminescent device of above method manufacture indicates in the following table：
The above result shows that a kind of metal iridium complex of the invention is applied in organic luminescent device, especially as
Dopant material shows the advantage that driving voltage is low, luminous efficiency is high, 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 (10)
1. a kind of metal iridium complex, which is characterized in that its general formula of molecular structure is as shown in I：
Wherein, X1、X2Independently selected from nitrogen-atoms, oxygen atom, sulphur atom or phosphorus atoms；
Y is oxygen atom, sulphur atom or NRa, the RaSelected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted
C1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl in one
Kind；
R1Selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C2~C10Alkenyl, substituted or unsubstituted
C2~C10Alkynyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C1~C10Boryl, replace or
Unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl, substituted or unsubstituted C2~C50Amino
One of；
R2~R3Independently selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Alkoxy, take
Generation or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50One of heteroaryl；
R4~R9Independently selected from hydrogen atom, halogen atom, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted
C1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl, replace or
Unsubstituted C2~C50One of amino or the R4、R5Connection cyclization or the R6~R9Middle adjacent pairs are connected to
Ring.
2. a kind of metal iridium complex according to claim 1, which is characterized in that X1And X2For nitrogen-atoms.
3. a kind of metal iridium complex according to claim 1, which is characterized in that its general formula of molecular structure is as shown in II：
Wherein, Z is oxygen atom, sulphur atom, NRaOr CRbRc, the Ra~RcIndependently selected from substituted or unsubstituted C1~C10's
Alkyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3
~C50One of heteroaryl；R10Selected from hydrogen atom, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1
~C10Alkoxy, substituted or unsubstituted C1~C10Boryl, substituted or unsubstituted C6~C50Aryl, replace or not
Substituted C3~C50Heteroaryl, substituted or unsubstituted C2~C50One of amino.
4. a kind of metal iridium complex according to claim 1, which is characterized in that Y is oxygen atom or sulphur atom.
5. a kind of metal iridium complex according to claim 1, which is characterized in that R1Selected from methyl, ethyl, isopropyl, uncle
Butyl, cyclohexyl, trimethylsilyl, phenyl, xenyl, naphthalene, amino, fluorenyl, carbazyl, acridinyl, pyridyl group, pyrazine
Base or triazine radical.
6. a kind of metal iridium complex according to claim 1, which is characterized in that R2~R3Independently selected from methyl, second
Base, isopropyl, tert-butyl, cyclohexyl, phenyl, xenyl, naphthalene, pyridyl group, pyrazinyl or triazine radical.
7. a kind of metal iridium complex according to claim 1, which is characterized in that the structure on the right side of metal iridium is following knot
One of structure：
8. a kind of metal iridium complex according to claim 1, which is characterized in that the complex of iridium is selected from as follows
Any one in chemical structure：
9. a kind of organic luminescent device, which is characterized in that the organic luminescent device includes cathode, anode and is placed in the cathode
One or more organic compound layers between the anode, it is any that the organic compound layer contains claim 1~8
A kind of metal iridium complex described in.
10. a kind of organic luminescent device according to claim 9, which is characterized in that the organic compound layer includes
Luminescent layer contains a kind of metal iridium complex according to any one of claims 1 to 8 in luminescent layer.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438521A (en) * | 2018-12-04 | 2019-03-08 | 吉林大学 | A kind of complex of iridium and its application |
| CN111777646A (en) * | 2020-07-28 | 2020-10-16 | 奥来德(上海)光电材料科技有限公司 | Organic phosphorus luminescent material, preparation method thereof and organic electroluminescent device |
| US11542278B1 (en) | 2020-05-05 | 2023-01-03 | Nuvalent, Inc. | Heteroaromatic macrocyclic ether chemotherapeutic agents |
| WO2023085123A1 (en) * | 2021-11-15 | 2023-05-19 | キヤノン株式会社 | Organic compound and organic light-emitting element |
| US11667649B2 (en) | 2020-05-05 | 2023-06-06 | Nuvalent, Inc. | Heteroaromatic macrocyclic ether chemotherapeutic agents |
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2018
- 2018-06-05 CN CN201810576303.6A patent/CN108912175A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438521A (en) * | 2018-12-04 | 2019-03-08 | 吉林大学 | A kind of complex of iridium and its application |
| CN109438521B (en) * | 2018-12-04 | 2021-04-16 | 吉林大学 | Iridium complex and application thereof |
| US11542278B1 (en) | 2020-05-05 | 2023-01-03 | Nuvalent, Inc. | Heteroaromatic macrocyclic ether chemotherapeutic agents |
| US11667649B2 (en) | 2020-05-05 | 2023-06-06 | Nuvalent, Inc. | Heteroaromatic macrocyclic ether chemotherapeutic agents |
| CN111777646A (en) * | 2020-07-28 | 2020-10-16 | 奥来德(上海)光电材料科技有限公司 | Organic phosphorus luminescent material, preparation method thereof and organic electroluminescent device |
| WO2023085123A1 (en) * | 2021-11-15 | 2023-05-19 | キヤノン株式会社 | Organic compound and organic light-emitting element |
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