CN109748938A

CN109748938A - Divalent platinum complex, its application and organic photoelectric device

Info

Publication number: CN109748938A
Application number: CN201910103064.7A
Authority: CN
Inventors: 杭晓春; 盛永健
Original assignee: Nanjing Tech University; AAC Optoelectronic Changzhou Co Ltd
Current assignee: Nanjing Tech University
Priority date: 2019-02-01
Filing date: 2019-02-01
Publication date: 2019-05-14
Anticipated expiration: 2039-02-01
Also published as: CN109748938B

Abstract

The invention belongs to electroluminescent organic material technical field, a kind of divalent platinum complex, its application and organic photoelectric device are provided.Divalent platinum complex provided by the present invention has chemical structure described in Formulas I, is a kind of blue light emitting material.This kind of blue light emitting material is used as dopant material in OLED luminescent device and equipment, and the blue peak issued is between 450-470nm.Benzimidazole type Cabbeen is introduced into the ligand structure of divalent platinum complex by the present invention, benzimidazole Cabbeen structure has suitable triplet energies, has more stable Carboplatin coordinate bond compared to nitrogen platinum coordinate bond, then has more stable excitation state conjugated system compared to imidazoles Cabbeen structure；Therefore, entire blue spectrum is narrower, and molecule is more stable in luminescence generated by light and Devices Electroluminescent, may advantageously facilitate the exploitation of blue light emitting material and improves the performance of luminescent device.

Description

Divalent platinum complex, its application and organic photoelectric device

Technical field

The present invention relates to optoelectronic materials technologies, more particularly to a kind of divalent platinum complex, its application and use Organic photoelectric device of this kind of divalent platinum complex as luminescent material.

Background technique

The compound that can be absorbed and/or shine is applicable to various optics and photoelectric device, including but not limited to such as Solar energy, photosensitive such light absorption device, Organic Light Emitting Diode (OLED), light emitting devices or existing light absorption have again The device of photoemissivity and related application for biomarker.In order to find for optics and electroluminescent device Organic and organo metallic material was specially made much to study in the art.It can be applied to the photoelectricity material to shine with illuminating device The research of material (red and green organometallic material is used as phosphor material, and blue organo metallic material is used as fluorescent material) takes Significant progress was obtained, and had been succeeded in Organic Light Emitting Diode (OLED) illumination and the application of advanced display. But, at present large-sized display devices that there is also luminescent lifetimes on is short, calorific value is big and actual efficiency is not high lacks Point.

It is generally believed that short wavelength's blue light (high energy blue light) of 400~450nm is that eye injury maximum can be produced Raw number visual fatigue and influence sleep eventually lead to eye pathologies harm and the human body of myopia, cataract and maculopathy Rhythm and pace of moving things harm.It designs the blue light source to shine in section between 450-500nm and is applied to relevant electronic product, Ke Yicong Solve the problems, such as the high energy blue light in nowadays electronic equipment to human injury in root.

However, excellent blue light emitting material is more rare, especially together for red and green luminescent material When the high efficiency phosphorescence blue light material molecule with rock-steady structure and suitable luminescent spectrum, have very big demand.With red And the minimum triplet excited state energy of green phosphor is compared, the minimum triplet excited state energy of blue phosphor is very high, this meaning Taste the minimum triplet excited state energy of the material of main part of blue device must be higher.Therefore, blue light emitting section can be reached Organic photoelectric device type is relatively limited, correspondingly, to regulate and control suitable blue spectrum, blue luminescent device is being shone It is then more difficult that outstanding performance is shown in the process.

Summary of the invention

The present invention provides one kind and is suitble to be used as emitter in Organic Light Emitting Diode (OLED), display and lighting engineering Divalent platinum complex.

Divalent platinum complex disclosed by the invention has structure described in formula (I):

Wherein, R^a、R^b、R^c、R^dAnd R^fIt is each independently monosubstituted or disubstituted, and R^a、R^b、R^c、R^dAnd R^fRespectively solely On the spot it is selected from monatomic substituent group or polyatom substituent group；The monatomic substituent group include hydrogen atom, its isotope atom or Halogen atom；The polyatom substituent group includes alkyl, the alkyl of aryl substitution, fluorine-substituted alkyl, aryl, alkyl substitution Aryl, aryl replace aryl, naphthenic base, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, hydroxyl, sulfydryl, nitro, cyanogen Base, isocyano group, sulfinyl, sulfonyl, carboxyl, diazanyl, single hydrocarbylamino, Dialkylamino, single arylamino, diaryl Amino, alkoxy, aryloxy group, halogenated alkyl, ester group, alkoxy carbonyl, amide groups, alkoxycarbonyl amino, aryloxycarbonyl Amino, sulfamoyl, carbamoyl, alkylthio group, urea groups, phosphinylidyne amido, silicyl, polymeric groups, or contain same position The above-mentioned substituent group of plain atom；R^eAlkyl, the fluorine-substituted alkyl, virtue replaced selected from the alkyl containing 2 or more carbon, aryl The aryl or naphthenic base that base, alkyl-substituted aryl, aryl replace.

Optionally, R^a、R^b、R^c、R^dAnd R^fIt is each independently selected from deuterium, tritium, fluorine, chlorine, bromine or iodine atom.

Optionally, R^a、R^b、R^c、R^dAnd R^fIt is each independently selected from hydrogen atom, methyl, benzyl, diphenyl methyl, triphen Ylmethyl；Ethyl, 2- phenylethyl, 2,2- phenylethyl, 2,2,2- trifluoroethyl；Propyl, isopropyl, 3,3,3- trifluoropropyl Base, 1,1,1,3,3,3- hexafluoro -2- propyl；Butyl, isobutyl group, hexafluoro isobutyl group, tert-butyl；Cyclopropyl, cyclobutyl, ring penta Base, cyclohexyl, suberyl；Phenyl, 2- aminomethyl phenyl, 2- isopropyl phenyl, 2- ethylphenyl, 4- aminomethyl phenyl, 4- isopropyl Phenyl, 4- ethylphenyl, 4- tert-butyl-phenyl, 2,3- 3,5-dimethylphenyl, 2,3- diethyl phenyl, 2,3- diisopropyl phenyl, 2,3- diisobutyl phenyl, 2,3- dicyclohexylphenylbismuthine, 2,3- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,3-, bis- ring of 2,3- Amyl phenyl, 2,4- 3,5-dimethylphenyl, 2,4- diethyl phenyl, 2,4- diisopropyl phenyl, 2,4- diisobutyl phenyl, 2, 4- dicyclohexylphenylbismuthine, 2,4- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,4-, 2,4- bicyclopentyl phenyl, 2,6- dimethyl Phenyl, 2,6- diethyl phenyl, 2,6- diisopropyl phenyl, 2,6- diisobutyl phenyl, 2,6- dicyclohexylphenylbismuthine, 2,6- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,6-, 2,6- bicyclopentyl phenyl, 3,5- 3,5-dimethylphenyl, 3,5- diethylbenzene Base, 3,5- diisopropyl phenyl, 3,5- diisobutyl phenyl, 3,5- dicyclohexylphenylbismuthine, 3,5- Bicyclopropyl phenyl, 3,5- Two cyclobutylphenyls, 3,5- bicyclopentyl phenyl, 2,3,5,6- tetramethylphenyl, 2,4,6- trimethylphenyl, tri- second of 2,4,6- Base phenyl, 2,4,6- triisopropyl phenyl, 2,4,6- triisobutyl phenyl, 2,4,6- thricyclohexyl phenyl, tri- cyclopropyl of 2,4,6- Base phenyl, tri- cyclobutylphenyl of 2,4,6-, tri- cyclopentyl phenyl of 2,4,6-.

Optionally, R^eSelected from benzyl, diphenyl methyl, trityl group；Ethyl, 2- phenylethyl, 2,2- phenyl second Base, 2,2,2- trifluoroethyl；Propyl, isopropyl, 3,3,3- trifluoro propyl, 1,1,1,3,3,3- hexafluoro -2- propyl；It is butyl, different Butyl, hexafluoro isobutyl group, tert-butyl；Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl；Phenyl, 2- aminomethyl phenyl, 2- Isopropyl phenyl, 2- ethylphenyl, 4- aminomethyl phenyl, 4- isopropyl phenyl, 4- ethylphenyl, 4- tert-butyl-phenyl, 2,3- bis- Aminomethyl phenyl, 2,3- diethyl phenyl, 2,3- diisopropyl phenyl, 2,3- diisobutyl phenyl, 2,3- dicyclohexylphenylbismuthine, 2,3- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,3-, 2,3- bicyclopentyl phenyl, 2,4- 3,5-dimethylphenyl, 2,4- diethyl Phenyl, 2,4- diisopropyl phenyl, 2,4- diisobutyl phenyl, 2,4- dicyclohexylphenylbismuthine, 2,4- Bicyclopropyl phenyl, 2, Bis- cyclobutylphenyl of 4-, 2,4- bicyclopentyl phenyl, 2,6- 3,5-dimethylphenyl, 2,6- diethyl phenyl, 2,6- diisopropyl benzene Base, 2,6- diisobutyl phenyl, 2,6- dicyclohexylphenylbismuthine, 2,6- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,6-, 2,6- Bicyclopentyl phenyl, 3,5- 3,5-dimethylphenyl, 3,5- diethyl phenyl, 3,5- diisopropyl phenyl, 3,5- diisobutyl benzene Base, 3,5- dicyclohexylphenylbismuthine, 3,5- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 3,5-, 3,5- bicyclopentyl phenyl, 2,3, 5,6- tetramethylphenyl, 2,4,6- trimethylphenyl, 2,4,6- triethyl group phenyl, 2,4,6- triisopropyl phenyl, 2,4,6- tri- Isobutyl phenenyl, 2,4,6- thricyclohexyl phenyl, tri- cyclopropyl-phenyl base of 2,4,6-, tri- cyclobutylphenyl of 2,4,6-, 2,4,6- tri- Cyclopentyl phenyl.

Optionally, R^a、R^b、R^c、R^dAnd R^fIt is each independently selected from deuterium ,-CDH₂、-CD₂H、-CD₃、-CDR¹R²、-CD₂R¹, Wherein, R¹And R²It is each independently selected from the virtue that alkyl, the alkyl that aryl replaces, aryl, alkyl-substituted aryl, aryl replace Base, naphthenic base, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, single hydrocarbylamino, Dialkylamino, single arylamino, two virtues Base amino, alkoxy, aryloxy group, halogenated alkyl, ester group, alkoxy carbonyl, amide groups, alkoxycarbonyl amino, aryloxy group carbonyl Base amino, sulfamoyl, carbamoyl, alkylthio group, urea groups, phosphinylidyne amido, silicyl, polymeric groups.

Optionally, R^eSelected from-CDR³R⁴、-CD₂R³, wherein R³And R⁴It is each independently selected from alkyl, the alkane that aryl replaces Base, aryl, alkyl-substituted aryl, the aryl of aryl substitution, naphthenic base, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, list Hydrocarbylamino, Dialkylamino, single arylamino, ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester group, alkoxy Carbonyl, amide groups, alkoxycarbonyl amino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio group, urea groups, phosphorus Amide groups, silicyl, polymeric groups.

Optionally, divalent platinum complex provided by the present invention has structure shown in formula (II) or formula (III):

Wherein, the R in formula (II)^aOr formula (III) R^dIt is each independently selected from alkyl, the alkyl, fluorine-substituted that aryl replaces Alkyl, aryl, alkyl-substituted aryl, aryl replace aryl, naphthenic base, cycloalkenyl, heteroaryl, alkenyl, silicyl, Polymeric groups, or the above-mentioned substituent group containing isotope atom；The R of formula (II)^b、R^c、R^d、R^fAnd R^eDefinition and logical formula (I) It is identical；R in formula (III)^b、R^c、R^a、R^fAnd R^eDefinition it is identical as logical formula (I).

Optionally, R^b、R^cAnd R^fFor hydrogen atom；R^aAnd R^dIt is each independently selected from methyl or hydrogen atom；R^eSelected from isopropyl Base, isobutyl group, 2,4,6- trimethylphenyl, 2,6- diisopropyl phenyl.

Optionally, divalent platinum complex provided by the present invention has the structure selected from one of following complex 1~75:

Embodiments of the present invention also provide above-mentioned divalent platinum complex as electroluminescent material or embedded photoluminescent material Application.

Optionally, the divalent platinum complex is blue light emitting material or phosphorescent light-emitting materials.Embodiments of the present invention The blue light wavelength peak value of provided divalent platinum complex is in the section 450~470nm, further, implementation of the invention The spectrum of the blue light of divalent platinum complex provided by mode is more than 50% in the section 450~490nm.

Embodiments of the present invention also provide a kind of organic photoelectric device comprising luminescent layer, and wrapped in the luminescent layer Containing above-mentioned divalent platinum complex.Optionally, the divalent platinum complex is shining in the luminescent layer of the organic photoelectric device Material, material of main part or guest materials.

In terms of existing technologies, embodiments of the present invention are by introducing the cooperation of divalent platinum for benzimidazole type Cabbeen The ligand of object, to provide a kind of new blue phosphorescent luminescent material.Since Cabbeen structure has suitable triplet energies And Carboplatin coordinate bond is more stable compared to nitrogen platinum coordinate bond, therefore obtained phosphor material has better stability.This Outside, the π system of polymorphic segment is excited in the increased ligand of benzimidazole type structure, is had more³LC ³π π * transition luminescence at Point, therefore, entire spectrum can narrow, this will promote to emit performance that is photochromic and improving device.In implementation of the invention In mode, the divalent platinum complex molecule of the disclosed neutral tetradentate ligands coordination containing benzimidazole Cabbeen platinum structure is made Can be with blue light-emitting for phosphorescent light-emitting materials, and have stability good, high-efficient, the section that shines is narrow and in long wavelength's blue light In section, entirely appropriate organic blue light emitters as in OLED Related product.In addition, embodiments of the present invention are mentioned Supply such compound is easily prepared and sublimation purification, be dissolved in common organic solvents, vapour deposition method and solwution method can be suitble to add simultaneously The device processing procedure of work.This kind of material emission performance has the characteristics that energy is low, high color purity, surmounts comprehensively in the prior art Various fluorescent materials will change the situation for lacking the blue light dopant material of stability and high efficiency in flat display field, while reach hair It is photochromic and improve the effect of device performance to penetrate blue light；This kind of stable complex provided by embodiments of the present invention shines Material, CIE coordinate and luminous efficiency more meet the demand of FPD.

Detailed description of the invention

Fig. 1 is luminescent spectrum figure of the complex 16 in solution and film in the specific embodiment of the invention；

Fig. 2 is luminescent spectrum figure of the complex 31 in solution and film in the specific embodiment of the invention；

Fig. 3 is luminescent spectrum figure of the complex 46 in solution and film in the specific embodiment of the invention；

Fig. 4 is the ultraviolet-visible absorption spectroscopy figure of the complex 16,31 and 61 in the specific embodiment of the invention；

Fig. 5 is the Frontier orbital distribution figure of the complex 16 in the specific embodiment of the invention；

Fig. 6 is the Frontier orbital distribution figure of the complex 46 in the specific embodiment of the invention；

Fig. 7 is the triplet excited states charge and hole distribution figure of the complex 16 in the specific embodiment of the invention；

Fig. 8 is the complex 16 in the specific embodiment of the invention¹H NMR nuclear magnetic spectrogram；

Fig. 9 is the complex 31 in the specific embodiment of the invention¹H NMR nuclear magnetic spectrogram；

Figure 10 is the complex 46 in the specific embodiment of the invention¹H NMR nuclear magnetic spectrogram；

Figure 11 is the mass spectrogram of the complex 31 in the specific embodiment of the invention；

Figure 12 is the mass spectrogram of the complex 46 in the specific embodiment of the invention；

Figure 13 is the purity phenogram after 31 sublimation purification of complex in the specific embodiment of the invention；

Figure 14 is the cross-section diagram of the OLED device in the specific embodiment of the invention；

Figure 15 is the luminescent spectrum that the device of complex 31 has been used in the specific embodiment of the invention；

Figure 16 is the electroluminescent spectrum section that the device of complex 31 has been used in the specific embodiment of the invention；

Figure 17 is the photoelectric conversion current efficiency that the device of complex 31 has been used in the specific embodiment of the invention；

Figure 18 is the power efficiency that the photoelectric conversion of device of complex 31 has been used in the specific embodiment of the invention；

Figure 19 is the stability of photoluminescence curve graph that the device of complex 31,46 has been used in the specific embodiment of the invention；

The excitation state electronics distribution map of complex 31 in Figure 20 specific embodiment of the invention.

Specific embodiment

Further illustrate that the present invention, these embodiments are only intended to illustrate the present invention below by embodiment and comparative example, The present invention is not limited to following embodiments.All modifying or equivalently replacing the technical solution of the present invention, without departing from this hair The range of bright technical solution should all cover within the protection scope of the present invention.By reference to described further below and wherein include Example, the present invention can be more easily to understand.

Compound

In certain specific embodiments of the invention, structure metal iridium-platinum complex shown in formula I is provided (referred to as Divalent platinum complex):

In certain specific embodiments of the invention, R^a、R^b、R^c、R^dAnd R^fBe each independently selected from deuterium, tritium, fluorine, chlorine, Bromine or iodine atom.

In certain specific embodiments of the invention, R^a、R^b、R^c、R^dAnd R^fBe each independently selected from hydrogen atom, methyl, Benzyl, diphenyl methyl, trityl group；Ethyl, 2- phenylethyl, 2,2- phenylethyl, 2,2,2- trifluoroethyl；Third Base, isopropyl, 3,3,3- trifluoro propyl, 1,1,1,3,3,3- hexafluoro -2- propyl；Butyl, isobutyl group, hexafluoro isobutyl group, tertiary fourth Base；Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl；Phenyl, 2- aminomethyl phenyl, 2- isopropyl phenyl, 2- ethylo benzene Base, 4- aminomethyl phenyl, 4- isopropyl phenyl, 4- ethylphenyl, 4- tert-butyl-phenyl, 2,3- 3,5-dimethylphenyl, 2,3- diethyl Phenyl, 2,3- diisopropyl phenyl, 2,3- diisobutyl phenyl, 2,3- dicyclohexylphenylbismuthine, 2,3- Bicyclopropyl phenyl, 2, Bis- cyclobutylphenyl of 3-, 2,3- bicyclopentyl phenyl, 2,4- 3,5-dimethylphenyl, 2,4- diethyl phenyl, 2,4- diisopropyl benzene Base, 2,4- diisobutyl phenyl, 2,4- dicyclohexylphenylbismuthine, 2,4- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,4-, 2,4- Bicyclopentyl phenyl, 2,6- 3,5-dimethylphenyl, 2,6- diethyl phenyl, 2,6- diisopropyl phenyl, 2,6- diisobutyl benzene Base, 2,6- dicyclohexylphenylbismuthine, 2,6- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,6-, 2,6- bicyclopentyl phenyl, 3,5- 3,5-dimethylphenyl, 3,5- diethyl phenyl, 3,5- diisopropyl phenyl, 3,5- diisobutyl phenyl, 3,5- dicyclohexyl benzene Base, 3,5- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 3,5-, 3,5- bicyclopentyl phenyl, 2,3,5,6- tetramethylphenyl, 2, 4,6- trimethylphenyl, 2,4,6- triethyl group phenyl, 2,4,6- triisopropyl phenyl, 2,4,6- triisobutyl phenyl, 2,4,6- Thricyclohexyl phenyl, tri- cyclopropyl-phenyl base of 2,4,6-, tri- cyclobutylphenyl of 2,4,6-, tri- cyclopentyl phenyl of 2,4,6-.

In certain specific embodiments of the invention, R^eSelected from benzyl, diphenyl methyl, trityl group；Ethyl, 2- phenylethyl, 2,2- phenylethyl, 2,2,2- trifluoroethyl；Propyl, isopropyl, 3,3,3- trifluoro propyl, 1,1,1,3,3, 3- hexafluoro -2- propyl；Butyl, isobutyl group, hexafluoro isobutyl group, tert-butyl；Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cycloheptyl Base；Phenyl, 2- aminomethyl phenyl, 2- isopropyl phenyl, 2- ethylphenyl, 4- aminomethyl phenyl, 4- isopropyl phenyl, 4- ethylo benzene Base, 4- tert-butyl-phenyl, 2,3- 3,5-dimethylphenyl, 2,3- diethyl phenyl, 2,3- diisopropyl phenyl, 2,3- diisobutyl Phenyl, 2,3- dicyclohexylphenylbismuthine, 2,3- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,3-, 2,3- bicyclopentyl phenyl, 2, 4- 3,5-dimethylphenyl, 2,4- diethyl phenyl, 2,4- diisopropyl phenyl, 2,4- diisobutyl phenyl, 2,4- dicyclohexyl benzene Base, 2,4- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,4-, 2,4- bicyclopentyl phenyl, 2,6- 3,5-dimethylphenyl, 2,6- bis- Ethylphenyl, 2,6- diisopropyl phenyl, 2,6- diisobutyl phenyl, 2,6- dicyclohexylphenylbismuthine, 2,6- Bicyclopropyl benzene Base, bis- cyclobutylphenyl of 2,6-, 2,6- bicyclopentyl phenyl, 3,5- 3,5-dimethylphenyl, 3,5- diethyl phenyl, 3,5- bis- are different Propyl phenyl, 3,5- diisobutyl phenyl, 3,5- dicyclohexylphenylbismuthine, 3,5- Bicyclopropyl phenyl, bis- cyclobutyl benzene of 3,5- Base, 3,5- bicyclopentyl phenyl, 2,3,5,6- tetramethylphenyl, 2,4,6- trimethylphenyl, 2,4,6- triethyl group phenyl, 2, 4,6- triisopropyl phenyl, 2,4,6- triisobutyl phenyl, 2,4,6- thricyclohexyl phenyl, tri- cyclopropyl-phenyl base of 2,4,6-, 2, Tri- cyclobutylphenyl of 4,6-, tri- cyclopentyl phenyl of 2,4,6-.

In certain specific embodiments of the invention, R^a、R^b、R^c、R^dAnd R^fIt is each independently selected from deuterium ,-CDH₂、- CD₂H、 -CD₃、-CDR¹R²、-CD₂R¹, wherein R¹And R²It is each independently selected from alkyl, alkyl, the aryl, alkane that aryl replaces Aryl that aryl that base replaces, aryl replace, naphthenic base, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, single hydrocarbylamino, Dialkylamino, single arylamino, ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester group, alkoxy carbonyl, amide Base, alkoxycarbonyl amino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio group, urea groups, phosphinylidyne amido, first Silylation, polymeric groups.

In certain specific embodiments of the invention, R^eSelected from-CDR³R⁴、-CD₂R³, wherein R³And R⁴Each independently It is aryl that alkyl, aryl, alkyl-substituted aryl, the aryl replaced selected from alkyl, aryl replaces, naphthenic base, cycloalkenyl, miscellaneous Aryl, alkenyl, alkynyl, amino, single hydrocarbylamino, Dialkylamino, single arylamino, ammonia diaryl base, alkoxy, fragrant oxygen Base, halogenated alkyl, ester group, alkoxy carbonyl, amide groups, alkoxycarbonyl amino, aryloxycarbonylamino, sulfamoyl, ammonia Base formoxyl, alkylthio group, urea groups, phosphinylidyne amido, silicyl, polymeric groups.

In certain specific embodiments of the invention, provided divalent platinum complex has shown in Formula II or formula III Structure:

In structural formula II, on the one hand, R^aFor the substituent group other than hydrogen atom, contraposition of the fixed site in pyridine N.It is another Aspect, R^b、R^c、R^dAnd R^fIt can indicate mono-substituted substituent group or disubstituted substituent R¹And R², disubstituted substitution Base R¹And R²It is independent deuterium, CDH₂、CD₂H、CD₃、CDR¹R², CD₂R¹, R¹And R²It is each independently selected from alkyl, aryl replaces Alkyl, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, aryl replace aryl, naphthenic base, cycloalkenyl, heteroaryl, Alkenyl, alkynyl, amino, single hydrocarbylamino, Dialkylamino, single arylamino, ammonia diaryl base, alkoxy, aryloxy group, halogen Substituted alkyl, ester group, alkoxy carbonyl, amide groups, alkoxycarbonyl amino, aryloxycarbonylamino, sulfamoyl, amino first Acyl group, alkylthio group, urea groups, phosphinylidyne amido, silicyl, polymeric groups.

Each R^eFor independent substituent groups more than 2 carbon, alkyl, alkyl, the fluorine-substituted alkane that aryl replaces can be Base, aryl, alkyl-substituted aryl, aryl replace aryl, naphthenic base, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, Single hydrocarbylamino, Dialkylamino, single arylamino, ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester group, alcoxyl Base carbonyl, amide groups, alkoxycarbonyl amino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio group, urea groups, Phosphinylidyne amido, silicyl, polymeric groups.

In structural formula III, on the one hand, R^dFor the substituent group other than hydrogen atom, phenyl ring of the fixed site in Pt-C is aligned. On the other hand, R^b、R^c、R^aAnd R^fIt can indicate mono-substituted substituent group or disubstituted substituent R¹And R², disubstituted to take For base R¹And R²It is independent deuterium, CDH₂、CD₂H、CD₃、CDR¹R², CD₂R¹, R¹And R²It is each independently selected from alkyl, aryl takes The alkyl in generation, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, the aryl of aryl substitution, naphthenic base, cycloalkenyl, heteroaryl Base, alkenyl, alkynyl, amino, single hydrocarbylamino, Dialkylamino, single arylamino, ammonia diaryl base, alkoxy, aryloxy group, Halogenated alkyl, ester group, alkoxy carbonyl, amide groups, alkoxycarbonyl amino, aryloxycarbonylamino, sulfamoyl, amino Formoxyl, alkylthio group, urea groups, phosphinylidyne amido, silicyl, polymeric groups.

In certain specific embodiments of the invention, R^b、R^cAnd R^fFor hydrogen atom；R^aAnd R^dIt is each independently selected from methyl Or hydrogen atom；R^eSelected from isopropyl, isobutyl group, 2,4,6- trimethylphenyl, 2,6- diisopropyl phenyl.

In other specific embodiments of the invention, provided divalent platinum complex, which has, is selected from following complex One of 1~75 structure:

In specific embodiment below of the invention, will with complex 16, complex 18, complex 21, complex 31, For complex 46 and complex 61, illustrate the synthetic method of divalent platinum complex provided by the present invention, property and its Performance when as luminescent material.

Wherein, complex 16 and 31 represents substituent R e as big hyte alkyl group；Complex 18 represent molecule most High occupied orbital (HOMO) holds substituted base to replace, representative structure formula II；Complex 21, which is represented, non-occupies rail in the minimum of molecule Road (LUMO) holds substituted base to replace, representative structure formula III；Structural formula II and III also has material property possessed by formula I, and It and is a kind of situation of complex shown in formula I.

The synthesis of compound

The various preparation methods of compound provided by the present invention are illustrative.These methods are for illustrating various systems Preparation Method, but its intention is not intended to be limited to any specific method, temperature, catalyst, concentration, reactant composition and other works Skill condition can change.

In CDCl₃Or DMSO-d₆In solution, recorded by Varian liquid Nuclear Magnetic Resonance¹HNMR (hydrogen nuclear magnetic resonance) With¹³C NMR (nuclear magnetic resonance of carbon) spectrum is 300,400 or 500MHz, and chemical shift is using remaining protonated solvent as base It is quasi-.If using CDCl₃As solvent, then recorded using tetramethylsilane (δ=0.00ppm) as interior reference¹H NMR (hydrogen Nuclear magnetic resonance) spectrum；Using CDCl₃(δ=77.00ppm) is recorded as interior reference¹³C NMR (nuclear magnetic resonance of carbon) spectrum. If using DMSO-d₆As solvent, then using remaining H₂O (δ=3.33ppm) is recorded as interior reference¹H NMR (hydrogen Nuclear magnetic resonance) spectrum；Using DMSO-d₆(δ=39.52ppm) is recorded as interior reference¹³C NMR (nuclear magnetic resonance of carbon) light Spectrum.Following abbreviation is for explaining¹The diversity of H NMR (hydrogen nuclear magnetic resonance): s=singlet, d=two-wire state, t=tri- Line state, tetra- line state of q=, five line state of p=, the multi-thread state of m=, br=wide.

Universal synthesis method:

Complex provided by the present invention can be synthesized by following general purpose routine, the specific steps are the coupling reaction of segment, The cyclization reaction and metal complexation reaction of phenylimidazole ring.

Wherein, R^a、R^b、R^c、R^d、R^eAnd R^fDefinition it is identical as Formulas I.

Embodiment 1

Complex 16 and its preparation

The synthesis of the bromo- 9- of 2- (2- pyridyl group) carbazole:

2- bromine carbazole 0001 (3.69g, 15mmol), 2- bromopyridine are successively added into the 48mL tube sealing with magnetic rotor 0002 (1.57mL, 16.5mmol), cuprous iodide (0.3mmL, 0.02equiv), 1- methylimidazole (0.3mmol, 1.2equiv), t-BuOLi (18mmol, 1.2equiv) and toluene (50mL), obtained mixture are bubbled 10 minutes through nitrogen After be heated to 120 DEG C stir 8 hours.It is cooled to room temperature, adds water quenching reaction, be extracted with ethyl acetate, merge organic phase, use After appropriate saturated sodium-chloride water solution washing plus anhydrous sodium sulfate is dry.Vacuum distillation removes solvent, and gained crude product is passed through Silica gel column chromatogram separating purification, eluant, eluent are petroleum ether: ethyl acetate=25: 1, obtain white solid, yield 93%.

The synthesis of 2- (3- Amino-phenol base) -9- (2- pyridyl group) carbazole 0005:

The bromo- 9- of 2- (2- pyridyl group) carbazole 0003 (1equiv), 3- Amino-phenol are added into the Shrek pipe of 25ml 0004 (1.2 equiv), cuprous iodide (10%), L-PROLINE (L-Pro, 20%), cesium carbonate (2equiv) and dimethyl sulfoxide (0.5M).Obtained mixture is bubbled 10 minutes with nitrogen, and is stirred 3 days at 120 DEG C.After the cooling period, water and acetic acid are added Ethyl ester (EA), and mixture is filtered.It adopts and is extracted with ethyl acetate water phase, and each organic phase is merged, cleaned, had with brine Machine mutually uses anhydrous Na₂SO₄It is dry.It is used as eluent using PE: EA=8: 1, solution obtained is purified by silica gel column chromatography, Obtain target product 0005 (brown viscous liquid, yield 75%).

The synthesis of the bromo- N- isopropyl-aniline 1102 of 2-:

8g o-bromoaniline 1101 is added in the solution of 150ml methylene chloride in 15ml acetone and 75ml acetic acid.At 0 DEG C Lower addition 6ml borane dimethylsulfide ethereal solution, is then stirred overnight at room temperature.25wt% ammonia spirit is added after fully reacting and adjusts pH To 8.After 50ml water is added, it is extracted with dichloromethane three times.Collect organic phase and, be spin-dried for dry with anhydrous sodium sulfate The crude product for closing object 1102 is directly used in next step (yellow oil, yield 95%).

The synthesis of phenylenediamine derivative 1103:

A seal pipe into glove box adds the bromo- N- of 2- (isopropyl)-aniline 1102 (1equiv), 2- (3- amino- Phenylol) -9- (2- pyridyl group) carbazole 0005 (1.1equiv), palladium acetate (5%), J-phos (2- (dicyclohexyl phosphino-) connection Benzene, 5%), sodium tert-butoxide (1.5equiv) and toluene (0.2M).After allowing mixture to be bubbled 15 minutes, it will be mixed at 130 DEG C Object is closed to heat 18 hours.After the cooling period, ethyl acetate is added, then filters mixture.It adopts and is extracted with ethyl acetate water phase, And by it is each it is organic mix, cleaned with brine, use anhydrous Na₂SO₄It is dry.It is used as eluent using PE: EA=6: 1, passes through silicon Glue-line is analysed to purify solution obtained, and eluent is spin-dried for, target product 1103 (clear yellow viscous liquid, yield 80%) is obtained.¹H NMR (300MHz, DMSO) δ 8.67 (d, J=3.6Hz, 1H), 8.20-8.16 (m, 2H), 8.06 (td, J=7.8,1.9 Hz, 1H), 7.73 (dd, J=8.10,3.60Hz, 2H), 7.65-7.38 (m, 6H), 7.12-6.85 (m, 8H), 6.60 (d, J= 7.80 Hz, 2H), 6.50-6.40 (m, 3H), 6.31-6.27 (m, 2H), 3.57-3.48 (m, 1H), 1.06 (d, J=6.30Hz, 6H). MS(ESI):485.27[M+H⁺]

The synthesis of Cabbeen hexafluorophosphate 1104:

Phenylenediamine derivative 1103 (1equiv), ammonium hexafluorophosphate (1.1equiv) and orthoformic acid are added into a tube sealing Triethyl (0.5M).120 DEG C are heated overnight.Ethyl acetate is added after being cooled to room temperature, yellow mercury oxide is precipitated, product is obtained by filtration 1104 (yellow solid, yields 60%).

The synthesis of complex 16:

Cabbeen hexafluorophosphate 1104 (1equiv), dichloro (1,5- cyclo-octadiene) platinum (II) (Pt are added in tube sealing (COD)Cl₂, 0.9equiv), sodium acetate (1.05equiv) and THF (0.5M).It is heated 3 days at 120 DEG C.It is cooled to room temperature After be spin-dried for, using DCM: PE=4: 1 be used as eluent, solution obtained is purified by silica gel column chromatography, obtain target production Object: complex 16 (glassy yellow powder, yield 38%)

¹H-NMR (300MHz, DMSO) δ 9.52 (d, J=5.70Hz, 1H), 8.40 (d, J=8.10Hz, 1H), 8.24- 8.03 (m, 5H), 7.91 (d, J=8.10Hz, 1H), 7.74 (d, J=7.80Hz, 1H), 7.51-7.39 (m, 4H), 7.31- 7.26 (m, 3H), 6.99 (d, J=9.00Hz, 1H), 5.34-5.25 (m, 1H), 1.99-1.91 (m, 3H), 1.50 (d, J= 6.30Hz,3H).MS (ESI):688.08[M+H⁺]

Embodiment 2

Complex 18 and its preparation

The synthesis of 2- (3- methyl -5- Amino-phenol base) -9- (2- pyridyl group) carbazole 0007:

The bromo- 9- of 2- (2- pyridyl group) carbazole 0003 (1equiv), 3- methyl -5- ammonia are added into the Shrek pipe of 25ml Base-phenol 0006 (1.2equiv), cuprous iodide (10%), L-PROLINE (L-Pro, 20%), cesium carbonate (2equiv) and two First sulfoxide (0.5M).Obtained mixture is bubbled 10 minutes with nitrogen, and is stirred 3 days at 120 DEG C.After the cooling period, water is added With ethyl acetate (EA), and mixture is filtered.It adopts and is extracted with ethyl acetate water phase, and each organic phase is merged, it is clear with brine It washes, organic phase anhydrous Na₂SO₄It is dry.It is used as eluent using PE: EA=8: 1, is purified by silica gel column chromatography obtained Solution obtains target product 0007 (brown viscous liquid, yield 75%).

The synthesis of the bromo- N- isopropyl-aniline 1102 of 2-:

The synthesis of phenylenediamine derivative 2103:

A seal pipe into glove box adds the bromo- N- of 2- (isopropyl)-aniline 1102 (1equiv), 2- (3- methyl- Amino-phenylol) -9- (2- pyridyl group) carbazole 0007 (1.1equiv), palladium acetate (5%), J-phos (2- (dicyclohexylphosphontetrafluoroborate Base) biphenyl, 5%), sodium tert-butoxide (1.5equiv) and toluene (0.2M).After allowing mixture to be bubbled 15 minutes, at 130 DEG C Mixture is heated 18 hours.After the cooling period, ethyl acetate is added, then filters mixture.It adopts and is extracted with ethyl acetate water Phase, and by it is each it is organic mix, cleaned with brine, use anhydrous Na₂SO₄It is dry.It is used as eluent using PE: EA=6: 1, is led to Silica gel column chromatography is crossed to purify solution obtained, eluent is spin-dried for, obtains target product 2103 (clear yellow viscous liquid, yield 80%).¹H NMR(500MHz,CDCl₃) δ 8.72-8.69 (m, 1H), 8.07 (d, J=8.00Hz, 1H), 8.04 (d, J= 12.80,1H), 7.91 (td, J=8.00,1.90Hz, 1H), 7.82 (d, J=8.20Hz, 1H), 7.62 (d, J=8.10Hz, 1H), 7.55 (d, J=1.80Hz, 1H), 7.42 (dd, J=11.3,4.1Hz, 1H), 7.34-7.28 (m, 2H), 7.12 (d, J =7.50Hz, 1H), 7.08 (t, J=7.70Hz, 1H), 7.03 (dd, J=8.40,2.0Hz, 1H), 6.70 (d, J= 8.00Hz, 1H), 6.64 (t, J=7.50Hz, 1H), 6.30-6.24 (m, 3H), 5.00 (s, 1H), 3.93 (br, 1H), 3.63 (hept, J=6.25Hz, 1H), 2.21 (s, 3H), 1.18 (d, J=6.30Hz, 6H)

The synthesis of Cabbeen hexafluorophosphate 2104:

Phenylenediamine derivative 2103 (1equiv), ammonium hexafluorophosphate (1.1equiv) and orthoformic acid are added into a tube sealing Triethyl (0.5M).120 DEG C are heated overnight.Ethyl acetate is added after being cooled to room temperature, yellow mercury oxide is precipitated, product is obtained by filtration 2104 (yellow solid, yields 60%).

The synthesis of complex 18:

Cabbeen hexafluorophosphate 2104 (1equiv), dichloro (1,5- cyclo-octadiene) platinum (II) (Pt are added in tube sealing (COD)Cl₂, 0.9equiv), sodium acetate (1.05equiv) and THF (0.5M).It is heated 3 days at 120 DEG C.It is cooled to room temperature After be spin-dried for, using DCM: PE=4: 1 be used as eluent, solution obtained is purified by silica gel column chromatography, obtain target production Object: complex 18 (glassy yellow powder, yield 38%).¹H NMR(500MHz,DMSO)δ9.55–9.52(m,1H),8.46 (d, J=8.30Hz, 1H), 8.28-8.20 (m, 2H), 8.18 (d, J=7.50Hz, 1H), 8.13 (d, J=8.10Hz, 1H), 8.05 (d, J=8.10Hz, 1H), 7.92 (d, J=8.2Hz, 1H), 7.59 (s, 1H), 7.55-7.40 (m, 5H), 7.34- 7.26 (m, 2H), 6.85 (s, 1H), 5.32 (hept, J=7.0Hz, 1H), 2.48 (s, 3H), 1.95 (d, J=6.50Hz, 3H), 1.53 (d, J=6.40Hz, 3H) .MS (ESI): 702.00 [M+H⁺]

Implement real column 3

Complex 21 and its preparation

The synthesis of the bromo- 9- of 2- (4- methyl -2- pyridyl group) carbazole:

2- bromine carbazole 0001 (1eqiv, 15mmol), the bromo- 4- of 2- are successively added into the 48mL tube sealing with magnetic rotor Picoline 0008 (1.1eqiv 16.5mmol), cuprous iodide (0.3mmL, 0.02equiv), 1- methylimidazole (0.3mmol, 1.2equiv), t-BuOLi (18mmol, 1.2equiv) and toluene (50mL), obtained mixture is through nitrogen drum Bubble is heated to 120 DEG C and stirs 8 hours after 10 minutes.It is cooled to room temperature, adds water quenching reaction, be extracted with ethyl acetate, be associated with Machine phase, after being washed with appropriate saturated sodium-chloride water solution plus anhydrous sodium sulfate is dry.Vacuum distillation removes solvent, and gained is thick Product is by silica gel column chromatogram separating purification, and eluant, eluent is petroleum ether: ethyl acetate=25: 1, obtain white solid, yield 93%.

The synthesis of 2- (3- Amino-phenol base) -9- (4- methyl -2- pyridyl group) carbazole 0010:

The bromo- 9- of 2- (4- methyl -2- pyridyl group) carbazole 0009 (1equiv), 3- ammonia is added into the Shrek pipe of 25ml Base-phenol 0004 (1.2equiv), cuprous iodide (10%), L-PROLINE (L-Pro, 20%), cesium carbonate (2equiv) and two First sulfoxide (0.5M).Obtained mixture is bubbled 10 minutes with nitrogen, and is stirred 3 days at 120 DEG C.After the cooling period, water is added With ethyl acetate (EA), and mixture is filtered.It adopts and is extracted with ethyl acetate water phase, and each organic phase is merged, it is clear with brine It washes, organic phase anhydrous Na₂SO₄It is dry.It is used as eluent using PE: EA=8: 1, is purified by silica gel column chromatography obtained Solution obtains target product 0010 (brown viscous liquid, yield 75%).

The synthesis of phenylenediamine derivative 3103:

A seal pipe into glove box adds the bromo- N- of 2- (isopropyl)-aniline 1102 (1equiv), 2- (3- amino- Phenylol) -9- (4- methyl -2- pyridyl group) carbazole 0010 (1.1equiv), palladium acetate (5%), J-phos (2- (dicyclohexyl Phosphino-) biphenyl, 5%), sodium tert-butoxide (1.5equiv) and toluene (0.2M).After allowing mixture to be bubbled 15 minutes, at 130 DEG C It is lower to heat mixture 18 hours.After the cooling period, ethyl acetate is added, then filters mixture.It adopts and is extracted with ethyl acetate Water phase, and by it is each it is organic mix, cleaned with brine, use anhydrous Na₂SO₄It is dry.It is used as eluent using PE: EA=6: 1, is led to Silica gel column chromatography is crossed to purify solution obtained, eluent is spin-dried for, obtains target product 3103 (clear yellow viscous liquid, yield 80%).¹H NMR(500MHz,CDCl₃) δ 8.55 (d, J=5.00Hz, 1H), 8.07 (d, J=8.1Hz, 1H), 8.04 (d, J =12.60Hz, 1H), 7.79 (d, J=8.20Hz, 1H), 7.52 (d, J=1.90Hz, 1H), 7.44-7.39 (m, 2H), 7.31 (t, J=7.40Hz, 1H), 7.15-7.04 (m, 4H), 7.03 (dd, J=8.40,2.0Hz, 1H), 6.73-6.62 (m, 2H), 6.48-6.41 (m, 3H), 5.06 (s, 1H), 3.95 (br, 1H), 3.63 (hept, J=6.3Hz, 1H), 2.48 (s, 3H), 1.18 (d, J=6.30Hz, 6H)

The synthesis of Cabbeen hexafluorophosphate 3104:

Phenylenediamine derivative 3103 (1equiv), ammonium hexafluorophosphate (1.1equiv) and orthoformic acid are added into a tube sealing Triethyl (0.5M).120 DEG C are heated overnight.Ethyl acetate is added after being cooled to room temperature, yellow mercury oxide is precipitated, product is obtained by filtration 3104 (yellow solid, yields 60%).

The synthesis of complex 21:

Cabbeen hexafluorophosphate 3104 (1equiv), dichloro (1,5- cyclo-octadiene) platinum (II) (Pt are added in tube sealing (COD)Cl₂, 0.9equiv), sodium acetate (1.05equiv) and THF (0.5M).It is heated 3 days at 120 DEG C.It is cooled to room temperature After be spin-dried for, using DCM: PE=4: 1 be used as eluent, solution obtained is purified by silica gel column chromatography, obtain target production Object: complex 21 (glassy yellow powder, yield 38%).¹H NMR (500MHz, DMSO) δ 9.39 (d, J=6.00Hz, 1H), 8.41 (d, J=8.20Hz, 1H), 8.17 (t, J=7.6Hz, 2H), 8.07-8.04 (m, 2H), 7.93 (d, J=8.20Hz, 1H), 7.75 (d, J=7.60Hz, 1H), 7.54-7.40 (m, 4H), 7.30 (dd, J=14.3,8.00Hz, 2H), 7.19 (d, J =5.90 Hz, 1H), 7.01 (d, J=8.00Hz, 1H), 5.37-5.30 (m, 1H), 2.46 (s, 3H), 1.96 (d, J= 6.50Hz, 3H), 1.53 (d, J=6.60Hz, 3H) .MS (ESI): 702.13 [M+H⁺]

Embodiment 4

The synthesis of complex 31

The synthesis of the bromo- N- isobutyl group-aniline 4102 of 2-:

8g o-bromoaniline 1101 is added in the solution of 150ml methylene chloride in 15ml acetone and 75ml acetic acid.At 0 DEG C Lower addition 6ml borane dimethylsulfide ethereal solution, is then stirred overnight at room temperature.25wt% ammonia spirit is added after fully reacting and adjusts pH To 8.After 50ml water is added, it is extracted with dichloromethane three times.Collect organic phase and, be spin-dried for dry with anhydrous sodium sulfate The crude product for closing object 4102 is directly used in next step (yellow oil, yield 96%).

The synthesis of phenylenediamine derivative 4103:

A seal pipe into glove box adds the bromo- N- of 2- (isopropyl)-aniline 4102 (1equiv), 2- (3- amino- Phenylol) -9- (2- pyridyl group) carbazole 0005 (1.1equiv), palladium acetate (5%), J-phos (2- (dicyclohexyl phosphino-) connection Benzene, 5%), sodium tert-butoxide (1.5equiv) and toluene (0.2M).After allowing mixture to be bubbled 15 minutes, it will be mixed at 130 DEG C Object is closed to heat 18 hours.After the cooling period, ethyl acetate is added, then filters mixture.It adopts and is extracted with ethyl acetate water phase, And by it is each it is organic mix, cleaned with brine, use anhydrous Na₂SO₄It is dry.It is used as eluent using PE: EA=6: 1, passes through silicon Glue-line is analysed to purify solution obtained, and eluent is spin-dried for, target product 4103 (clear yellow viscous liquid, yield 84%) is obtained.¹H NMR (300MHz, DMSO) δ 8.67 (dd, J=4.80,1.20Hz, 1H), 8.22-8.14 (m, 2H), 8.10-8.04 (m, 1H), 7.73 (dd, J=8.4,3.0Hz, 2H), 7.46-7.43 (m, 1H), 7.40-7.37 (m, 2H), 7.31 (m, 1H), 7.26 (m, 1H), 7.08-7.03 (m, 1H), 6.99-6.89 (m, 3H), 6.56 (d, J=7.50Hz, 1H), 6.46 (d, J= 7.40Hz, 1H), 6.39 (d, J=8.70Hz, 1H), 6.30-6.28 (m, 2H), 4.59 (t, J=5.90Hz, 1H), 2.81 (dd, J=6.60,5.90Hz, 2H), 1.82-1.68 (m, 1H), 0.81 (d, J=6.60Hz, 6H) .MS (ESI): 499.35 [M +H⁺]

The synthesis of Cabbeen hexafluorophosphate 4104:

Phenylenediamine derivative 4103 (1equiv), ammonium hexafluorophosphate (1.1equiv) and orthoformic acid are added into a tube sealing Triethyl (0.5M).120 DEG C are heated overnight.Ethyl acetate is added after being cooled to room temperature, yellow mercury oxide is precipitated, product is obtained by filtration 4104 (yellow solid, yields 67%).

The synthesis of complex 31:

Cabbeen hexafluorophosphate 4104 (1equiv), dichloro (1,5- cyclo-octadiene) platinum (II) (Pt are added in tube sealing (COD)Cl₂, 0.9equiv), sodium acetate (1.05equiv) and THF (0.5M).It is heated 3 days at 120 DEG C.It is cooled to room temperature After be spin-dried for, using DCM: PE=4: 1 be used as eluent, solution obtained is purified by silica gel column chromatography, obtain target production Object: complex 31 (glassy yellow powder, yield 39%).¹H NMR (300MHz, DMSO) δ 9.67 (d, J=5.70Hz, 1H), 8.35 (d, J=7.20Hz, 1H), 8.30-8.19 (m, 2H), 8.18 (d, J=7.50Hz, 1H), 8.05 (d, J=8.10Hz, 1H), 7.90 (s, 1H), 7.87 (s, 1H), 7.73 (d, J=7.50Hz, 1H), 7.51-7.38 (m, 4H), 7.31-7.18 (m, 3H), 6.99 (d, J=8.10Hz, 1H), 4.33 (t, J=7.0Hz, 2H), 2.40-2.27 (m, 1H), 0.69-0.58 (m, 6H).MS(ESI): 702.12[M+H⁺]

Embodiment 5

The synthesis of complex 46:

The synthesis of phenylenediamine derivative 5102:

A seal pipe into glove box adds o-dibromobenzene 5101 (1equiv), 2- (3- Amino-phenol base) -9- (2- pyridyl group) carbazole 0005 (1.1equiv), palladium acetate (5%), J-phos (2- (dicyclohexyl phosphino-) biphenyl, 5%), uncle Sodium butoxide (1.5equiv) and toluene (0.2M).After allowing mixture to be bubbled 15 minutes, mixture is heated 18 at 130 DEG C Hour.After the cooling period, ethyl acetate is added, then filters mixture.It adopts and is extracted with ethyl acetate water phase, and will be each organic It mixes, is cleaned with brine, use anhydrous Na₂SO₄It is dry.It is used as eluent using PE: EA=6: 1, by silica gel column chromatography come net Change solution obtained, eluent is spin-dried for, obtains target product 5102 (yellow viscous liquid, yield 78%).¹H NMR (500MHz,CDCl₃) δ 8.70 (d, J=3.50Hz, 1H), 8.07 (dd, J=8.5,4.0Hz, 2H), 7.92 (m, 1H), 7.81 (d, J=8.50Hz, 1H), 7.63 (d, J=8.00Hz, 1H), 7.59 (d, J=2.00Hz, 1H), 7.52-7.50 (m, 1H), 7.44-7.41 (m, 1H), 7.34-7.28 (m, 3H), 7.23 (d, J=8.00Hz, 1H), 7.14 (t, J=7.70Hz, 1H), 7.05 (dd, J=8.40,2.00Hz, 1H), 6.86-6.84 (m, 2H), 6.76-6.72 (m, 1H), 6.69-6.67 (m, 1H), 6.07(s, 1H).MS(ESI):508.14[M+H⁺]

The synthesis of phenylenediamine derivative 5104:

A seal pipe into glove box adds 2,4,6- trimethyl-aniline 5103 (1equiv), 2- (3- (N-2- bromine Phenyl)-phenylol) -9- (2- pyridyl group) carbazole 5102 (1.1equiv), palladium acetate (5%), J-phos (2- (dicyclohexyl Phosphino-) biphenyl, 5%), sodium tert-butoxide (1.5equiv) and toluene (0.2M).After allowing mixture to be bubbled 15 minutes, at 130 DEG C It is lower to heat mixture 18 hours.After the cooling period, ethyl acetate is added, then filters mixture.It adopts and is extracted with ethyl acetate Water phase, and by it is each it is organic mix, cleaned with brine, use anhydrous Na₂SO₄It is dry.It is used as eluent using PE: EA=6: 1, is led to Silica gel column chromatography is crossed to purify solution obtained, eluent is spin-dried for, obtains target product 5104 (clear yellow viscous liquid, yield 87%).¹H NMR (300MHz, DMSO) δ 8.65 (dd, J=4.90,1.20Hz, 1H), 8.18 (dd, J=7.80,5.30Hz, 2H), 8.05 (td, J=8.10,1.90Hz, 1H), 7.72 (t, J=7.10Hz, 2H), 7.44-7.37 (m, 4H), 7.30 (t, J =7.10Hz, 1H), 7.11 (t, J=8.10Hz, 1H), 7.08-7.02 (m, 1H), 6.99 (dd, J=8.50,2.10Hz, 1H), 6.86 (s, 2H), 6.76 (t, J=7.10Hz, 1H), 6.59-6.43 (m, 2H), 6.41-6.30 (m, 2H), 6.23 (s, 1H), 5.92 (d, J=6.90 Hz, 1H), 2.20 (s, 3H), 1.97 (s, 6H) .MS (ESI): 561.34 [M+H⁺]

The synthesis of Cabbeen hexafluorophosphate 5105:

Phenylenediamine derivative 5104 (1equiv), ammonium hexafluorophosphate (1.1equiv) and orthoformic acid are added into a tube sealing Triethyl (0.5M).120 DEG C are heated overnight.Ethyl acetate is added after being cooled to room temperature, yellow mercury oxide is precipitated, product is obtained by filtration 5105 (yellow solid, yields 61%).

The synthesis of complex 46:

Cabbeen hexafluorophosphate 5105 (1equiv), dichloro (1,5- cyclo-octadiene) platinum (II) (Pt are added in tube sealing (COD)Cl₂, 0.9equiv), sodium acetate (1.05equiv) and THF (0.5M).It is heated 3 days at 120 DEG C.It is cooled to room temperature After be spin-dried for, using DCM: PE=4: 1 be used as eluent, solution obtained is purified by silica gel column chromatography, obtain target production Object: complex 46 (glassy yellow powder, yield 32%).¹H NMR (300MHz, DMSO) δ 8.63 (d, J=10.8Hz, 1H), 8.43 (d, J=8.2Hz, 1H), 8.11 (d, J=7.40Hz, 1H), 8.03 (d, J=8.7Hz, 1H), 7.95 (d, J=8.3Hz, 1H), 7.92-7.79 (m, 3H), 7.56-7.16 (m, 7H), 7.10-6.90 (m, 3H), 6.53 (t, J=6.4Hz, 1H), 2.28 (s, 3H),2.11(s,6H).MS(ESI):763.09[M⁺]

Embodiment 6

Complex 61 and its preparation

The synthesis of phenylenediamine derivative 6102:

A seal pipe into glove box adds 2,6- diisopropyl base-aniline 6101 (1equiv), 2- (3- (N-2- Bromophenyl)-phenylol) -9- (2- pyridyl group) carbazole 5102 (1.1equiv), palladium acetate (5%), J-phos (2- (two hexamethylenes Base phosphino-) biphenyl, 5%), sodium tert-butoxide (1.5equiv) and toluene (0.2M).After allowing mixture to be bubbled 15 minutes, 130 Mixture is heated 18 hours at DEG C.After the cooling period, ethyl acetate is added, then filters mixture.It is mentioned using ethyl acetate Fetch water phase, and by it is each it is organic mix, cleaned with brine, use anhydrous Na₂SO₄It is dry.It is used as eluent using PE: EA=6: 1, Solution obtained is purified by silica gel column chromatography, eluent is spin-dried for, and obtains target product 6102 (clear yellow viscous liquid, yield 84%).¹H NMR(500MHz,CDCl₃) δ 8.68 (d, J=4.80Hz, 1H), 8.06 (t, J=8.15Hz, 2H), 7.92- 7.87 (m, 1H), 7.81 (d, J=8.30Hz, 1H), 7.61 (d, J=8.15Hz, 1H), 7.56 (d, J=1.5Hz, 1H), 7.42 (t, J=7.5 Hz, 1H), 7.33 (t, J=7.5Hz, 1H), 7.29-7.24 (m, 1H), 7.24-7.09 (m, 5H), 7.05 (dd, J=8.40,2.00 Hz, 1H), 6.96 (s, 1H), 6.70 (s, 1H), 6.60-6.44 (m, 3H), 6.23 (d, J= 6.70Hz, 1H), 3.19-3.03 (m, 2H), 1.11 (d, J=5.30Hz, 12H) .MS (ESI): 603.36 [M+H⁺]

The synthesis of Cabbeen hexafluorophosphate 6103:

Phenylenediamine derivative 6102 (1equiv), ammonium hexafluorophosphate (1.1equiv) and orthoformic acid are added into a tube sealing Triethyl (0.5M).120 DEG C are heated overnight.Ethyl acetate is added after being cooled to room temperature, yellow mercury oxide is precipitated, product is obtained by filtration 6103 (yellow solid, yields 56%).

Complex 61 synthesizes:

Cabbeen hexafluorophosphate 6103 (1equiv), dichloro (1,5- cyclo-octadiene) platinum (II) (Pt are added in tube sealing (COD)Cl₂, 0.9equiv), sodium acetate (1.05equiv) and THF (0.5M).It is heated 3 days at 120 DEG C.It is cooled to room temperature After be spin-dried for, using DCM: PE=4: 1 be used as eluent, solution obtained is purified by silica gel column chromatography, obtain target production Object: complex 61 (glassy yellow powder, yield 33%).¹H NMR (300MHz, DMSO) δ 8.67 (d, J=5.80Hz, 1H), 8.43 (d, J=8.20Hz, 1H), 8.10 (d, J=7.60Hz, 1H), 8.00 (d, J=8.50Hz, 1H), 7.84 (t, J= 9.30Hz, 4H), 7.58-7.17 (m, 9H), 7.04 (t, J=8.7Hz, 2H), 6.33 (t, J=6.5Hz, 1H), 2.93 (br, 2H),1.09(s,6H), 0.86(s,6H).MS(ESI):806.09[M+H⁺]

The characterization of compound

The emission spectrum of divalent platinum complex of the invention shows that, when adding D-atom to aglucon, triplet state energy gap is several It is identical.

The representative data of emitter excitation purity can be from using 5%PMMA (polymethyl methacrylate) dichloromethane solution The film emission spectrum of preparation obtains.Table 1 is the emission spectra data of complex.In table 1 below, λ is peak wavelength, FWHM For half-peak breadth, 450-700nm is the ratio of integral of the emission spectrum in the section 450-500nm, and CIE (x, y) is according to the world The chromaticity coordinate parameter of illumination committee standard.Complex 16,18,21,31,46,61 is obtained prepared by the embodiment of the present invention Peak wavelength between 455-456, half-peak breadth is between 19-28nm.In the blue light emitting region 450- for meeting Vision Health Spectrum accounting within 500nm interval range reaches 70% or more.Also, four example divalent platinum complexes are all in dark blue light Within luminous section (x < 0.15, y < 0.15), wherein complex 16,21,31,46 and 61 reaches pure blue light material standard (X= 0.14, Y=0.10)；Low energy, the characteristic of narrow spectrum ensure that this kind of divalent platinum complex becomes extremely outstanding blue light material Material.

1 emission spectra data of table

Complex	λ/nm	FWHM/nm	450-500nm/%	CIE(x,y)
					Complex 16	458	28	74.1	(0.137,0.109)
Complex 18	457	31	68.6	(0.138,0.132)
					Complex 21	450	18	64.9	(0.145,0.078)
Complex 31	456	26	75.1	(0.136,0.107)
					Complex 46	455	19	73.4	(0.137,0.090)
Complex 61	455	19	77.4	(0.137,0.090)

In addition, relevant drawings are described as follows:

Attached drawing 1-3 successively respectively illustrates luminescent spectrum figure of the divalent platinum complex 16,31 and 46 in solution and film； Under 340nm ultraviolet excitation, three complexs between 450-500nm, are gathering in the emission wavelength in dichloromethane solution Emission wavelength in methyl methacrylate (PMMA) between 450-480nm, all complex wavelength in deep blue light region, And the half-peak breadth of spectrum is relatively narrow, illustrates that the series complex is good blue emitting material.Wherein, Fig. 1 shows divalent The emission peak of the emission spectrum in PMMA film of platinum complex 16 is 458nm, half-peak breadth 28nm, wherein in effective blue light Number of photons in section is more than 75%.

Attached drawing 4 shows ultravioletvisible absorption light of the above-mentioned divalent platinum complex 16,31 and 61 in dichloromethane solution Spectrogram, according to abosrption spectrogram it is recognised that the absorption spectrum absorbs very strong, the absorption in the long-wavelength region section 280-420nm Region is different from ligand precursor.Wherein, 280-330nm can be attributed to the π-π * transition in complex centered on carbazole,. Wherein 330nm later absorption peak can be attributed to the transfer transition of the valence state between complex central metallic ions and ligand (MLCT) transition.This part transition shows very by force on this kind of divalent platinum complex, and kurtosis can achieve ligand and absorb kurtosis Half, extinction coefficient can achieve 2.5 × 10^-4·M^-1·cm^-1.This point illustrates that the energy absorption of such molecule is very high Effect, can be used as the preferred molecular structure of dopant material molecule.Wavelength 300nm or less is the π π * that cyclic ligand spin allows Transition, wavelength 300nm-340nm are the π π * transition of carbazole ligand part；The absorption of wavelength 340nm or more is arrived from metal The d π * transition of the transfer state of ligand.Wherein, the absorption peak between 300-400nm with¹LC(¹π π *) transition is related, and absorbs Band is very strong, illustrates that the series compound has the very strong π π * transition centered on ligand, is ground according to the correlation of preceding citation Study carefully as a result, this effect help to obtain the blue light emitters that luminescent spectrum is relatively narrow, excitation purity is high.Similarly, wherein Absorption peak between 400-430 and metal shift to ligand charge (¹MLCT) transition is related, and absorption band is also very strong, explanation The series compound has very strong¹MLCT effect, according to correlation theory (Yersin, H.；Finkenzeller, W.J.Triplet Emitters for Organic Light-Emitting Diodes:Basic Properties； 2008.), this effect can increase the phosphorescence luminous efficiency of molecule, and this kind of complex molecule can be used as phosphorescent devices doping material The preferred molecule of material.

To the band gap of divalent platinum complex 16,18,21,31,46,61 provided by embodiments of the present invention and related light It is as follows to learn property representation:

Band gap magnitude (the E of material_g), LUMO and HOMO value measured using cyclic voltammetry (CV).Entire test process is in hand It is carried out on CHI600D electrochemical workstation (Shanghai Chen Hua instrument company) in casing (Lab2000, Etelux), is with Pt column Working electrode, using Ag/AgCl as reference electrode, Pt for auxiliary electrode constitute three-electrode system, test process use medium It is 0.1M hexafluorophosphoric acid 4-butyl amine (Bu₄NPF₆) dimethylformamide (DMF) solution, surveyed potential is with the two of addition cyclopentadienyls Iron (Fc) is used as internal standard.λ is the peak wavelength of divalent platinum complex dissolution in methylene chloride in following table, and FWHM is its half-peak Width, the triplet state photon energy (E of material_T1) by 1240/ λ of formula_0→1Calculate (λ_0→1For the first vibration under the conditions of 77K Peak), unit is electronics Ford (eV).

Table 2 is the energy level data of complex.From the data of table 2 it is found that the energy level of the HOMO track of complex 16,46,61 It is lower than complex 31, illustrate that the HOMO energy level of material can be improved on the position benzimidazole N long chain alkylating.Complex 46 and 61 lumo energy is lower than the lumo energy of complex 16 and 31, this explanation introduces aryl substituent on benzimidazole Lumo energy can be improved.The triplet energy state of four divalent platinum complexes is unanimously 2.76eV, this mainly has with mother nucleus structure It closes, illustrates that triplet state radiation transistion is with uniformity in the case where low temperature condition i.e. molecular thermalmotion limitation.This also says Bright, these divalent platinum complexes can be by introducing substituent group to the tune within its energy level and its emission spectrum progress small range Control, to obtain optimal luminescent spectrum section.

2 energy level data of table

Complex	E_HOMO/eV	E_LUMO/eV	Eg/eV	λ/nm	E_T1/eV
						Complex 16	-5.37	-2.31	3.06	458	2.76
Complex 18	-5.28	-2.27	3.01	458	2.76
						Complex 21	-5.35	-2.17	3.18	451	2.79
Complex 31	-5.32	-2.27	3.05	459	2.76
						Complex 46	-5.36	-2.19	3.17	456	2.76
Complex 61	-5.38	-2.21	3.17	456	2.76

Attached drawing 5 shows the Frontier orbital distribution of complex 16, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) it is distributed.HOMO and LUMO is shown as isolated mode, wherein HOMO track is mainly distributed on phenoxy group carbazole and two On the hexa-atomic becket of valence platinum central atom new life, LUMO is more evenly distributed in pyridine and benzimidazole and platinum center The Pt-C key of Atomic coordinate, this says that Pt-C coordinate bond has armaticity in this structure of name, is conducive to the stabilization of molecular structure.

Attached drawing 6 shows the Frontier orbital distribution of complex 46, and the mode and Fig. 5 that HOMO and LUMO are shown as isolated are aobvious 16 main part of complex shown is identical, and wherein HOMO track is mainly distributed on phenoxy group carbazole and divalent platinum central atom is new On raw hexa-atomic becket, LUMO major part is more evenly distributed in pyridine and benzimidazole and platinum central atom and matches The Pt-C key of position, LUMO another part are distributed on a small quantity in delocalization to entire molecule, this explanation passes through substituent R^eVariation, can To regulate and control the excitation state orbit distribution of complex molecule, to obtain complex molecule knot more stable in optical physics conversion process Structure.

Attached drawing 7 describes the triplet excited states charge and hole distribution of complex 21, in conjunction with the front rail of complex 16 Road illustrates that the track for having multiple groups high level participates in the first excited state of triplet state, is formed in the different electronics of singlet point The process of cloth, this charge delocalization formed in crossing process between the gap that singlet to triplet state converts is known as delocalization list → tri- Line state spin transformation (Delocalized Spin Transition, DST) mechanism, it is evident that representative complex 16 processes with the transformation of DST mechanism, this process are that state charge is excited to be transferred to carbazole and N- phenylbenzimidazol from pyridine end On fragment structure, to be formed more³LC(³π π *) transition ingredient, lead to small excitation state structure of variation and final The limited narrow luminescent spectrum of vibration.

In addition, compound structure characterization relevant drawings are described as follows:

Attached drawing 8 is the monomolecular of complex 16¹H nuclear magnetic spectrum is composed by hydrogen and illustrates that the complex can independently be stablized Ground exists and can be with separating-purifying and characterization.From nuclear magnetic spectrum, in addition to the divalent platinum complex has stable structure Except characterization, divalent platinum complex does not show the signal of accumulation shape, illustrates such divalent platinum complex under solution state Molecule is existing for the state of unimolecule separation.

Attached drawing 9 is the monomolecular of complex 31¹H nuclear magnetic spectrum is composed by hydrogen and illustrates that the complex can independently be stablized Ground exists and can be with separating-purifying and characterization.From nuclear magnetic spectrum, in addition to the divalent platinum complex has stable structure Except characterization, divalent platinum complex does not show the signal of accumulation shape, illustrates such divalent platinum complex under solution state Molecule is existing for the state of unimolecule separation.

Attached drawing 10 is the monomolecular of complex 46¹H nuclear magnetic spectrum is composed by hydrogen and illustrates that the complex can independently be stablized Ground exists and can be with separating-purifying and characterization.From nuclear magnetic spectrum, in addition to the divalent platinum complex has stable structure Except characterization, divalent platinum complex does not show the signal of accumulation shape, illustrates such divalent platinum complex under solution state Molecule is existing for the state of unimolecule separation.

Attached drawing 11 is the mass spectral characteristi figure of the molecule of complex 31.Mass spectroscopy molecular shows that molecular signal shows that M/C peak value is 701.18, it is consistent with the molecular ion peak of compound 31, illustrate that the complex structure is design structure.

Attached drawing 12 is the mass spectral characteristi figure of the molecule of complex 46.Mass spectroscopy molecular shows that molecular signal shows that M/C peak value is 763.09, it is consistent with the molecular ion peak of compound 46, illustrate that the complex structure is design structure.

Attached drawing 13 is the ultrahigh pressure liquid phase purity analysis figure of complex 31 after purification.Changing liquid phase purity is 100%, explanation The compound can obtain the product of ultra-high purity by purification, be suitble to technology controlling and process.

Device example

Device architecture and performance

Attached drawing 14 shows the cross-section diagram of OLED luminescent device 1000, which includes disclosed herein a kind of two Valence platinum complex.OLED device 1000 includes matrix 1002, anode layer 1004, hole transmission layer 1006, luminescent layer 1008, electricity Sub- transport layer 1010 and metal cathode layer 1012.Anode 1004 is usually transparent material, such as tin indium oxide.Luminescent layer 1008 can be the luminescent material including an emitter and a main body.Wherein EIL refers to electron injecting layer, can be considered as electronics biography A part of defeated layer 1010.HIL is hole injection layer, can be considered as a part of hole transmission layer 1006.CPL covers for cathode Cap rock.Complex 101 disclosed herein is used in 1008 luminescent layers as blue light emitting dopant material.Divalent platinum complex is done When being used in OLED device for dopant material, device is prepared by spin-coating method, structure ITO/PEDOT: PSS (70nm)/main body Material: divalent platinum complex (1000-x: x, 40nm)/DPEPO (10nm)/TmPyPB (50nm)/Liq (1 nm)/Al (100nm)。

In above-mentioned specific embodiment, luminescent layer 1008 may include of the invention one or more provided by the present invention Divalent platinum complex, optionally related a kind of material of main part.ETL layer 1010 and HTL 1006 also may include a kind of or more Kind of divalent platinum complex and with the hand-to-hand another implanted layer of electricity.The material of implanted layer may include EIL (electron injecting layer), HIL (hole injection layer) and CPL (cathode coating), form can be simple layer or be dispersed in electronics or hole transport material In material.Material of main part can be any suitable material of main part known in the art.The luminescent color of OLED is by luminescent layer The luminous energies (optical energy gap) of 1008 materials determines, can as described above by tuning transmitting divalent platinum complex and/ Or the electronic structure of material of main part tunes the luminous energy (optical energy gap) of 1008 material of luminescent layer.Sky in htl layer 1006 Electron transport material in hole transport materials and ETL layer 1010 may include that any suitable hole as known in the art passes Defeated body.

Phosphorescence can be presented in divalent platinum complex provided by embodiments of the present invention.Phosphorescent OLED (has phosphorescence The OLED of emitter) general other OLED than such as fluorescence OLED etc are with higher device efficiency.In " nature " 1998 The 151-154 pages of 395 phase of year illustrates the luminescent device based on electroluminescent phosphorescence emitter, in WO2000/070655 in more detail Ground illustrates the luminescent device based on electroluminescent phosphorescence emitter, because it comprises about the interior of OLED (especially fluorescence OLED) Hold, is hereby incorporated by reference in the application.

Other device luminescent properties relevant drawings are described as follows:

Attached drawing 15 shows the luminescent spectrum of the device using complex 31.Illustrate that structure is ITO/PEDOT in figure: PSS (70nm)/2,6-MCPy: complex 31 (95: 5,40nm)/DPEPO (10nm)/TmPyPB (50nm)/Liq (1nm)/Al The luminescent spectrum of (100nm) OLED.It is shown, is shone according to the electroluminescent spectrum of the device of the complex of luminescent layer doping 5% With respect to its luminescence generated by light peak red shift 5nm in PMMA medium, half-peak breadth is suitable, maintains emitting complexes 31 itself at peak The characteristics of luminescence, it is CIE (0.15,0.18) that its chromaticity coordinate value, which is calculated, illustrates that this device issues dark blue light.

Attached drawing 16 shows the electroluminescent spectrum section using the device of complex 31, illustrates that structure is ITO/ PEDOT: PSS (70nm)/2,6-MCPy: complex 101 (95: 5,40nm)/DPEPO (10nm)/TmPyPB (50nm)/Liq The integrated normalized figure of the luminescent spectrum of (1nm)/Al (100nm) OLED.It is shown according to normalization integral, the thorn less than 450nm The ingredient for swashing property blue light only has 4.5%, 70.2% photon energy in 500nm or more.Belonged to according to traditional blue light, Blue photons between 450-500nm account for the 65.7% of the number of all transmitting photons.

Attached drawing 17 shows the current efficiency in the device photoelectric conversion using complex 31, and wherein device architecture is ITO/PEDOT: PSS (70nm)/2,6-MCPy: complex 31 (100-x: x, 40nm)/DPEPO (10nm)/TmPyPB (50nm)/Liq (1nm)/Al (100nm) OLED, the accounting 2% and 5% in emitting layer material of complex 31.31 device of complex The once now highly stable curve of part photoelectric conversion current efficiency, from 0mA/cm²To 20mA/cm²Under current density change, electric current rolling Drop is less than 15%, and the device efficiency with higher of the dopant material, wherein the device of 2% and 5% doping is in 10mA/ cm²Current efficiency is respectively 11.5 and 13.4cd/A, illustrate complex 31 as blue light emitting dopant material have it is efficient, The light conversion performance of stabilized illumination.

Attached drawing 18 shows the power efficiency in the device photoelectric conversion using complex 31, device architecture ITO/ PEDOT: PSS (70nm)/2,6-MCPy: complex 31 (100-x: x, 40nm)/DPEPO (10nm)/TmPyPB (50nm)/ Liq (1nm)/Al (100nm) OLED, the accounting 2% and 5% in emitting layer material of complex 31.The wherein device of 2% doping The power efficiency of middle interception is in 1147cd/m²It is 10lm/W under brightness, the power efficiency intercepted in the device of 5% doping exists 1341cd/m²Illustrate that complex 31 has efficiently, surely as blue light emitting dopant material under brightness for 12.1lm/W and 5% Surely luminous light conversion performance.

Attached drawing 19 is shown using the device of complex 31,46 in 0.3mW/cm²375nm UV light irradiates lower luminous intensity With the variation of time, illustrate that being able to maintain within the device 400 minutes under strong luminescent condition decaying is no more than 5%, the light in 6 hours Less than 1%, such compound of this description of test has fabulous stability of photoluminescence for spectrum decaying.

Attached drawing 20 shows the excitation state electronics distribution of complex 31, it can be seen that from S₁→T₁Negative electrical charge in crossing process Distribution changes, and the distribution in carbazole segment increases, to increase triplet state³π π *, this is obtained for this kind of compound design Obtain the excitation state internal characteristics of narrow emission spectrum, the referred to as mechanism of delocalization spin transformation, English name Delocalized Spin Transition (DST)。

Device preparation

The preparation step (being prepared with common process in the art) of the following OLED luminescent device of structure described briefly below: ITO/PEDOT: PSS (70nm)/MCP: complex 101 (95: 5,40nm)/DPEPO (10nm)/TmPyPB (50 nm)/Liq (1nm)/Al(100nm)。

Crucible equipped with OLED organic material and the crucible equipped with metal aluminum shot are placed sequentially in organic evaporating source and nothing Machine evaporates on source position.Close cavity, just vacuumize with pumping high vacuum step so that vapor deposition inside OLED evaporated device Vacuum degree reach 10E^-7Torr.OLED evaporation film-forming method: opening OLED organic evaporating source, carries out to OLED organic material 100 DEG C of preheatings, preheating time are 15 minutes, guarantee further to remove the steam in OLED organic material.Then to needing to be deposited Organic material carry out the heat treatment that is rapidly heated, and the baffle above evaporation source is opened, until the evaporation source of the material has Machine material is run out of, while when crystal-vibration-chip detector detects evaporation rate, then slowly being heated up, and increasing extent of temperature is 1-5 DEG C, When evaporation rate was stablized at 1A/ seconds, the baffle immediately below mask plate is opened, OLED film forming is carried out, when computer end observes When organic film on ito substrate reaches default film thickness, baffle right above mask plate baffle and evaporation source is closed, it is organic to close this The evaporation source heater of material.The evaporation process of other organic materials and cathodic metal material is as described above.Encapsulation uses UV ring Oxygen resin carries out photocuring encapsulation.Sample after encapsulation carries out IVL performance test, and IVL equipment uses Mc Science M6100 It is tested.

The performance data of the above-mentioned luminescent device being prepared is as shown in table 3.

3 device luminescent properties of table

It is as shown in table 3 the luminescent properties data comparison of each luminescent device.The electroluminescence wavelength of luminescent device mainly by The decision of divalent platinum complex luminescence generated by light itself, the purity and electroluminescent of divalent platinum complex photoluminescence spectra itself Spectral purity it is directly related.Under identical conditions, the efficiency of luminescent device is also luminous with divalent platinum complex itself Quantum efficiency trend is consistent, the spectrum colour of the lower transmitting light of luminous excitation purity and dopant material light itself excitation of luminescent device Purity is directly linked.In the electroluminescent spectrum and film of divalent platinum complex luminescent device photo luminescent devices compare it is found that Compared to film photoluminescence spectra, the slightly red shift of the electroluminescent spectrum of luminescent device, but peak wavelength is still located at blue region (460-470nm), spectrum also largely is located in blue light range, and the chromaticity coordinate of calculating illustrates that the luminescent device belongs to ethereal blue Light luminescent device.Since most of light is all in blue light section, it is thus only necessary to which the light for filtering out a small amount of long wavelength illustrates of the invention Complex material provided by embodiment can fully meet the coloration of the pure blue light CIE (0.14,0.08) in display It is required that.

It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention, And in practical applications, can to it, various changes can be made in the form and details, without departing from spirit and model of the invention It encloses.

Claims

1. a kind of divalent platinum complex, which is characterized in that have structure shown in Formulas I:

Wherein,

R^a、R^b、R^c、R^dAnd R^fIt is each independently monosubstituted or disubstituted, and R^a、R^b、R^c、R^dAnd R^fIt is each independently selected from list Replacing group or polyatom substituent group；The monatomic substituent group includes hydrogen atom, its isotope atom or halogen atom；Institute Stating polyatom substituent group includes that alkyl, the aryl alkyl, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, the aryl that replace take Aryl, naphthenic base, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, hydroxyl, sulfydryl, nitro, cyano, isocyano group, the sulfurous in generation Acyl group, sulfonyl, carboxyl, diazanyl, single hydrocarbylamino, Dialkylamino, single arylamino, ammonia diaryl base, alkoxy, fragrant oxygen Base, halogenated alkyl, ester group, alkoxy carbonyl, amide groups, alkoxycarbonyl amino, aryloxycarbonylamino, sulfamoyl, ammonia Base formoxyl, alkylthio group, urea groups, phosphinylidyne amido, silicyl, polymeric groups, or the above-mentioned substitution containing isotope atom Base；

R^eSelected from the alkyl containing 2 or more carbon, aryl replace alkyl, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, The aryl or naphthenic base that aryl replaces.

2. divalent platinum complex according to claim 1, which is characterized in that R^a、R^b、R^c、R^dAnd R^fIt is each independently selected from Deuterium, tritium, fluorine, chlorine, bromine or iodine atom.

3. divalent platinum complex according to claim 1, which is characterized in that R^a、R^b、R^c、R^dAnd R^fIt is each independently selected from Hydrogen atom, methyl, benzyl, diphenyl methyl, trityl group；Ethyl, 2- phenylethyl, 2,2- phenylethyl, 2,2,2- Trifluoroethyl；Propyl, isopropyl, 3,3,3- trifluoro propyl, 1,1,1,3,3,3- hexafluoro -2- propyl；Butyl, isobutyl group, hexafluoro Isobutyl group, tert-butyl；Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl；Phenyl, 2- aminomethyl phenyl, 2- cumene Base, 2- ethylphenyl, 4- aminomethyl phenyl, 4- isopropyl phenyl, 4- ethylphenyl, 4- tert-butyl-phenyl, 2,3- 3,5-dimethylphenyl, 2,3- diethyl phenyl, 2,3- diisopropyl phenyl, 2,3- diisobutyl phenyl, 2,3- dicyclohexylphenylbismuthine, bis- cyclopropyl of 2,3- Base phenyl, bis- cyclobutylphenyl of 2,3-, 2,3- bicyclopentyl phenyl, 2,4- 3,5-dimethylphenyl, 2,4- diethyl phenyl, 2,4- bis- Isopropyl phenyl, 2,4- diisobutyl phenyl, 2,4- dicyclohexylphenylbismuthine, 2,4- Bicyclopropyl phenyl, bis- cyclobutyl benzene of 2,4- Base, 2,4- bicyclopentyl phenyl, 2,6- 3,5-dimethylphenyl, 2,6- diethyl phenyl, 2,6- diisopropyl phenyl, bis- isobutyl of 2,6- Base phenyl, 2,6- dicyclohexylphenylbismuthine, 2,6- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,6-, 2,6- bicyclopentyl phenyl, 3, 5- 3,5-dimethylphenyl, 3,5- diethyl phenyl, 3,5- diisopropyl phenyl, 3,5- diisobutyl phenyl, 3,5- dicyclohexyl benzene Base, 3,5- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 3,5-, 3,5- bicyclopentyl phenyl, 2,3,5,6- tetramethylphenyl, 2,4, 6- trimethylphenyl, 2,4,6- triethyl group phenyl, 2,4,6- triisopropyl phenyl, 2,4,6- triisobutyl phenyl, 2,4,6- tri- Cyclohexyl phenyl, tri- cyclopropyl-phenyl base of 2,4,6-, tri- cyclobutylphenyl of 2,4,6-, tri- cyclopentyl phenyl of 2,4,6-.

4. divalent platinum complex according to claim 1, which is characterized in that R^eSelected from benzyl, diphenyl methyl, triphen Ylmethyl；Ethyl, 2- phenylethyl, 2,2- phenylethyl, 2,2,2- trifluoroethyl；Propyl, isopropyl, 3,3,3- trifluoropropyl Base, 1,1,1,3,3,3- hexafluoro -2- propyl；Butyl, isobutyl group, hexafluoro isobutyl group, tert-butyl；Cyclopropyl, cyclobutyl, ring penta Base, cyclohexyl, suberyl；Phenyl, 2- aminomethyl phenyl, 2- isopropyl phenyl, 2- ethylphenyl, 4- aminomethyl phenyl, 4- isopropyl Phenyl, 4- ethylphenyl, 4- tert-butyl-phenyl, 2,3- 3,5-dimethylphenyl, 2,3- diethyl phenyl, 2,3- diisopropyl phenyl, 2,3- diisobutyl phenyl, 2,3- dicyclohexylphenylbismuthine, 2,3- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,3-, bis- ring of 2,3- Amyl phenyl, 2,4- 3,5-dimethylphenyl, 2,4- diethyl phenyl, 2,4- diisopropyl phenyl, 2,4- diisobutyl phenyl, 2,4- Dicyclohexylphenylbismuthine, 2,4- Bicyclopropyl phenyl, bis- cyclobutylphenyl of 2,4-, 2,4- bicyclopentyl phenyl, 2,6- dimethyl benzene Base, 2,6- diethyl phenyl, 2,6- diisopropyl phenyl, 2,6- diisobutyl phenyl, 2,6- dicyclohexylphenylbismuthine, bis- ring of 2,6- Propyl phenyl, bis- cyclobutylphenyl of 2,6-, 2,6- bicyclopentyl phenyl, 3,5- 3,5-dimethylphenyl, 3,5- diethyl phenyl, 3,5- Diisopropyl phenyl, 3,5- diisobutyl phenyl, 3,5- dicyclohexylphenylbismuthine, 3,5- Bicyclopropyl phenyl, bis- cyclobutyl of 3,5- Phenyl, 3,5- bicyclopentyl phenyl, 2,3,5,6- tetramethylphenyl, 2,4,6- trimethylphenyl, 2,4,6- triethyl group phenyl, 2, 4,6- triisopropyl phenyl, 2,4,6- triisobutyl phenyl, 2,4,6- thricyclohexyl phenyl, tri- cyclopropyl-phenyl base of 2,4,6-, 2, Tri- cyclobutylphenyl of 4,6-, tri- cyclopentyl phenyl of 2,4,6-.

5. divalent platinum complex according to claim 1, which is characterized in that R^a、R^b、R^c、R^dAnd R^fIt is each independently selected from Deuterium ,-CDH₂、-CD₂H、-CD₃、-CDR¹R²、-CD₂R¹, wherein R¹And R²Be each independently selected from alkyl, aryl replace alkyl, Aryl, alkyl-substituted aryl, the aryl of aryl substitution, naphthenic base, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, single alkyl Amino, Dialkylamino, single arylamino, ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester group, alkoxy carbonyl, Amide groups, alkoxycarbonyl amino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio group, urea groups, phosphamide Base, silicyl, polymeric groups.

6. divalent platinum complex according to claim 1, which is characterized in that R^eSelected from-CDR³R⁴、-CD₂R³, wherein R³With R⁴It is each independently selected from aryl, cycloalkanes that alkyl, the alkyl that aryl replaces, aryl, alkyl-substituted aryl, aryl replace Base, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, single hydrocarbylamino, Dialkylamino, single arylamino, ammonia diaryl base, Alkoxy, aryloxy group, halogenated alkyl, ester group, alkoxy carbonyl, amide groups, alkoxycarbonyl amino, aryloxycarbonylamino, Sulfamoyl, carbamoyl, alkylthio group, urea groups, phosphinylidyne amido, silicyl, polymeric groups.

7. divalent platinum complex according to claim 1, which is characterized in that the divalent platinum complex has Formula II or formula Structure shown in III:

Wherein,

R in Formula II^aOr the R in formula III^dIt is each independently selected from alkyl, alkyl, the fluorine-substituted alkyl, virtue that aryl replaces Base, alkyl-substituted aryl, the aryl of aryl substitution, naphthenic base, cycloalkenyl, heteroaryl, alkenyl, silicyl, polymer matrix Group, or the above-mentioned substituent group containing isotope atom；

R in Formula II^b、R^c、R^d、R^fAnd R^eDefinition it is identical as Formulas I；R in formula III^a、R^b、R^c、R^fAnd R^eDefinition and Formulas I phase Together.

8. divalent platinum complex according to claim 1, which is characterized in that R^b、R^cAnd R^fFor hydrogen atom；R^aAnd R^dRespectively solely On the spot it is selected from methyl or hydrogen atom；R^eSelected from isopropyl, isobutyl group, 2,4,6- trimethylphenyl, 2,6- diisopropyl phenyl.

9. divalent platinum complex according to claim 1, which is characterized in that have selected from one of following complex 1~75 Structure:

10. divalent platinum complex described in any one of claims 1 to 9 is as electroluminescent material or embedded photoluminescent material Using.

11. application according to claim 10, which is characterized in that the divalent platinum complex is blue light emitting material or phosphorus Light luminescent material.

12. a kind of organic photoelectric device, which is characterized in that including luminescent layer, and include claim 1 to 9 in the luminescent layer Any one of described in divalent platinum complex.

13. organic photoelectric device according to claim 12, which is characterized in that the divalent platinum complex is described organic Luminescent material, material of main part or guest materials in the luminescent layer of electrooptical device.