CN109748938A - Bivalent platinum complex, application thereof and organic photoelectric device - Google Patents

Abstract

The invention belongs to the technical field of organic electroluminescent materials, and provides a divalent platinum complex, its application and an organic photoelectric device. The divalent platinum complex provided by the present invention has the chemical structure described in formula I, and is a blue light emitting material. The blue light emitting material is used as a doping material in OLED light emitting devices and equipment, and the blue light emitted by the blue light has a peak value between 450-470 nm. In the present invention, the benzimidazole carbene is introduced into the ligand structure of the divalent platinum complex, and the benzimidazole carbene structure has suitable triplet energy, and has more stable carbon-platinum coordination bonds compared with nitrogen-platinum coordination bonds. Compared with the imidazole carbene structure, it has a more stable excited state conjugated system; therefore, the entire blue light spectrum is narrower, and the molecule is more stable in photoluminescence and device electroluminescence, which is conducive to promoting the development and improvement of blue light emitting materials. performance of light-emitting devices.

Description

Divalent platinum complexes, their applications and organic optoelectronic devices

technical field

The present invention relates to the technical field of optoelectronic materials, in particular to a divalent platinum complex, its application and an organic optoelectronic device using the divalent platinum complex as a light-emitting material.

Background technique

Compounds capable of absorbing and/or emitting light may be suitable for use in various optical and optoelectronic devices, including but not limited to light absorbing devices such as solar energy, photosensitive, organic light emitting diodes (OLEDs), light emitting devices, or both light absorbing and light emitting devices Emitter capable devices and related applications for biomarkers. Much research has been devoted to the discovery of organic and organometallic materials for optical and electroluminescent devices. Significant progress has been made in the research of optoelectronic materials (red and green organometallic materials used as phosphorescent materials, blue organometallic materials used as fluorescent materials) that can be applied to light-emitting and lighting devices, and has been used in organic light-emitting diode (OLED) lighting. and advanced display applications. However, there are still shortcomings such as short luminous life, large heat generation and low actual efficiency in the application of large-size display devices.

It is generally believed that the short-wavelength blue light (high-energy blue light) of 400-450 nm is the most harmful to the eyes, can cause digital visual fatigue and affect sleep, and eventually lead to eye pathological hazards and human rhythm hazards such as myopia, cataract and macular degeneration. Designing a blue light source with a luminous range between 450-500nm and applying it to related electronic products can fundamentally solve the problem of harm to human body caused by high-energy blue light in today's electronic equipment.

However, compared with red and green light-emitting materials, excellent blue light-emitting materials are scarce, especially high-efficiency phosphorescent blue-light material molecules with stable structure and suitable light-emitting spectrum at the same time, there is a great demand. The lowest triplet state energy of the blue phosphor is high compared to the lowest triplet state energy of the red and green phosphors, which means that the lowest triplet state energy of the host material for the blue device must be higher. Therefore, the types of organic optoelectronic devices that can reach the blue light emission range are relatively limited, and accordingly, it is more difficult to control the appropriate blue light spectrum so that the blue light emitting device exhibits excellent performance during the light emission process.

SUMMARY OF THE INVENTION

The present invention provides a divalent platinum complex suitable for use as an emitter in organic light emitting diode (OLED), display and lighting technologies.

The divalent platinum complex disclosed in the present invention has the structure described in formula (I):

wherein R ^a , R ^b , R ^c , R ^d and R ^f are each independently mono- or di-substituted, and R ^a , R ^b , R ^c , R ^d and R ^f are each independently selected from monoatomic substituents or polyatomic substituents; the monoatomic substituents include hydrogen atoms, isotopic atoms or halogen atoms thereof; the polyatomic substituents include alkyl, aryl-substituted alkyl, fluorine-substituted alkyl, aryl, alkane aryl substituted aryl, aryl substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, hydroxyl, mercapto, nitro, cyano, isocyano, sulfinyl , sulfonyl, carboxyl, hydrazine, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, amido, alkane Oxycarbonylamino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramido, silyl, polymer groups, or the aforementioned substituents containing isotopic atoms; R ^e Selected from an alkyl group containing 2 or more carbons, an aryl-substituted alkyl group, a fluorine-substituted alkyl group, an aryl group, an alkyl-substituted aryl group, an aryl-substituted aryl group, or a cycloalkyl group.

Alternatively, ^Ra , ^Rb , ^Rc , ^Rd and ^Rf are each independently selected from deuterium, tritium, fluorine, chlorine, bromine or iodine atoms.

Alternatively, R ^a , R ^b , R ^c , R ^d and R ^f are each independently selected from a hydrogen atom, methyl, benzyl, diphenylmethyl, triphenylmethyl; ethyl, 2- Phenylethyl, 2,2-phenylethyl, 2,2,2-trifluoroethyl; propyl, isopropyl, 3,3,3-trifluoropropyl, 1,1,1,3 ,3,3-hexafluoro-2-propyl; butyl, isobutyl, hexafluoroisobutyl, tert-butyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl; benzene base, 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-ethylphenyl, 4-tert-butyl phenyl, 2,3-dimethylphenyl, 2,3-diethylphenyl, 2,3-diisopropylphenyl, 2,3-diisobutylphenyl, 2,3- Dicyclohexylphenyl, 2,3-dicyclopropylphenyl, 2,3-dicyclobutylphenyl, 2,3-dicyclopentylphenyl, 2,4-dimethylphenyl, 2 ,4-diethylphenyl, 2,4-diisopropylphenyl, 2,4-diisobutylphenyl, 2,4-dicyclohexylphenyl, 2,4-dicyclopropylbenzene base, 2,4-dicyclobutylphenyl, 2,4-dicyclopentylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diiso Propylphenyl, 2,6-diisobutylphenyl, 2,6-dicyclohexylphenyl, 2,6-dicyclopropylphenyl, 2,6-dicyclobutylphenyl, 2, 6-Dicyclopentylphenyl, 3,5-dimethylphenyl, 3,5-diethylphenyl, 3,5-diisopropylphenyl, 3,5-diisobutylphenyl , 3,5-dicyclohexylphenyl, 3,5-dicyclopropylphenyl, 3,5-dicyclobutylphenyl, 3,5-dicyclopentylphenyl, 2,3,5, 6-Tetramethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl, 2,4,6 -Triisobutylphenyl, 2,4,6-tricyclohexylphenyl, 2,4,6-tricyclopropylphenyl, 2,4,6-tricyclobutylphenyl, 2,4, 6-Tricyclopentylphenyl.

Optionally, ^Re is selected from benzyl, diphenylmethyl, triphenylmethyl; ethyl, 2-phenylethyl, 2,2-phenylethyl, 2,2,2-triphenylmethyl Fluoroethyl; propyl, isopropyl, 3,3,3-trifluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl; butyl, isobutyl, hexafluoropropyl Fluoroisobutyl, tert-butyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl; phenyl, 2-methylphenyl, 2-isopropylphenyl, 2-ethyl Phenyl, 4-methylphenyl, 4-isopropylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 2,3-dimethylphenyl, 2,3-diethyl Phenyl, 2,3-diisopropylphenyl, 2,3-diisobutylphenyl, 2,3-dicyclohexylphenyl, 2,3-dicyclopropylphenyl, 2,3- Dicyclobutylphenyl, 2,3-dicyclopentylphenyl, 2,4-dimethylphenyl, 2,4-diethylphenyl, 2,4-diisopropylphenyl, 2 ,4-diisobutylphenyl, 2,4-dicyclohexylphenyl, 2,4-dicyclopropylphenyl, 2,4-dicyclobutylphenyl, 2,4-dicyclopentyl phenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,6-diisobutylphenyl, 2,6-diisopropylphenyl Cyclohexylphenyl, 2,6-dicyclopropylphenyl, 2,6-dicyclobutylphenyl, 2,6-dicyclopentylphenyl, 3,5-dimethylphenyl, 3, 5-diethylphenyl, 3,5-diisopropylphenyl, 3,5-diisobutylphenyl, 3,5-dicyclohexylphenyl, 3,5-dicyclopropylphenyl , 3,5-dicyclobutylphenyl, 3,5-dicyclopentylphenyl, 2,3,5,6-tetramethylphenyl, 2,4,6-trimethylphenyl, 2 ,4,6-triethylphenyl, 2,4,6-triisopropylphenyl, 2,4,6-triisobutylphenyl, 2,4,6-tricyclohexylphenyl, 2 , 4,6-tricyclopropylphenyl, 2,4,6-tricyclobutylphenyl, 2,4,6-tricyclopentylphenyl.

Alternatively, ^Ra , ^Rb , ^Rc , ^Rd and ^Rf are each ^{independently} selected from _deuterium , ^-CDH2 , _-CD2H , _-CD3 , _-CDR1R2 , ^-CD2R1 , wherein R ¹ and R ² are each independently selected from alkyl, aryl-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl , alkenyl, alkynyl, amino, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, amido, alkane Oxycarbonylamino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramido, silyl, polymer groups.

Optionally, R ^e is selected from -CDR ³ R ⁴ , -CD ₂ R ³ , wherein R ³ and R ⁴ are each independently selected from alkyl, aryl-substituted alkyl, aryl, and alkyl-substituted aryl aryl, aryl-substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, alkoxy , aryloxy, haloalkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio, urea, phosphoramido, Silyl group, polymer group.

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

wherein, R in formula (II ⁾ or R in ^formula (III) is independently selected from alkyl, aryl-substituted alkyl, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, aryl Substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, silyl, polymeric groups, or the aforementioned substituents containing isotopic atoms; R ^b , R ^c , R of formula (II) The definitions of ^d , R ^f and ^Re are the same as those of the general formula (I); the definitions of R ^b , R ^c , R ^a , R ^f and ^Re in the formula (III) are the same as those of the general formula (I).

Optionally, R ^b , R ^c and R ^f are hydrogen atoms; R ^a and R ^d are each independently selected from methyl or hydrogen atoms; R ^e is selected from isopropyl, isobutyl, 2,4,6- Trimethylphenyl, 2,6-diisopropylphenyl.

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

Embodiments of the present invention also provide applications of the above-mentioned divalent platinum complexes as electroluminescent materials or photoluminescent materials.

Optionally, the divalent platinum complex is a blue light emitting material or a phosphorescent light emitting material. The blue light wavelength peak of the divalent platinum complex provided by the embodiment of the present invention is in the range of 450-470 nm, and further, the blue light spectrum of the divalent platinum complex provided by the embodiment of the present invention exceeds 50% at 450 nm. ~490nm range.

Embodiments of the present invention also provide an organic optoelectronic device, which includes a light-emitting layer, and the light-emitting layer includes the above-mentioned divalent platinum complex. Optionally, the divalent platinum complex is a light-emitting material, a host material or a guest material in the light-emitting layer of the organic optoelectronic device.

Compared with the prior art, the embodiments of the present invention provide a new blue phosphorescent light-emitting material by introducing a benzimidazole-type carbene into a ligand of a divalent platinum complex. Since the carbene structure has suitable triplet energy and the carbon-platinum coordination bond is more stable than the nitrogen-platinum coordination bond, the obtained phosphorescent material has better stability. In addition, the π system of the excited state part in the ligand with the increased benzimidazole type structure has more ³ LC ³ ππ* transition luminescence components, therefore, the whole spectrum can be narrowed, which will be able to promote the emission color and improve the device performance. In the embodiments of the present invention, the disclosed divalent platinum complex molecules coordinated by neutral tetradentate ligands containing a benzimidazocarbene platinum structure can emit blue light as a phosphorescent light-emitting material, and have good stability and efficiency. It has a narrow emission range and is in the range of long-wavelength blue light, which is completely suitable as an organic blue light emitter in OLED related products. In addition, the compounds provided by the embodiments of the present invention are easy to prepare, sublime and purify, dissolve in common organic solvents, and are suitable for device manufacturing processes of both evaporation method and solution method. This kind of material has the characteristics of low energy and good color purity, and comprehensively surpasses various fluorescent materials in the prior art. It will change the situation of the lack of stable and efficient blue light doping materials in the field of flat panel display, and at the same time achieve the emission of blue light color. And improve the device performance; the stable complex luminescent material provided by the embodiment of the present invention, its CIE coordinates and luminous efficiency are more in line with the needs of flat panel display.

Description of drawings

Fig. 1 is the luminescence spectrum diagram of the complex 16 in the solution and thin film in the specific embodiment of the present invention;

Fig. 2 is the luminescence spectrum diagram of the complex 31 in the solution and thin film in the specific embodiment of the present invention;

Fig. 3 is the luminescence spectrum diagram of complex 46 in solution and thin film in the specific embodiment of the present invention;

Fig. 4 is the ultraviolet-visible absorption spectrogram of the complexes 16, 31 and 61 in the specific embodiment of the present invention;

Fig. 5 is the front-line orbital distribution diagram of complex 16 in the specific embodiment of the present invention;

Fig. 6 is the front-line orbital distribution diagram of complex 46 in the specific embodiment of the present invention;

7 is a triplet excited state charge and hole distribution diagram of complex 16 in a specific embodiment of the present invention;

Fig. 8 is the ¹ H NMR nuclear magnetic spectrum of the complex 16 in the specific embodiment of the present invention;

Fig. 9 is the ¹ H NMR nuclear magnetic spectrum of complex 31 in the specific embodiment of the present invention;

Fig. 10 is the ¹ H NMR nuclear magnetic spectrum of complex 46 in the specific embodiment of the present invention;

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

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

Fig. 13 is the purity characterization diagram of the complex 31 after sublimation purification in the specific embodiment of the present invention;

14 is a cross-sectional view of an OLED device in an embodiment of the present invention;

Fig. 15 is the luminescence spectrum of the device using complex 31 in the specific embodiment of the present invention;

Fig. 16 is the electroluminescence spectral range of the device using complex 31 in the specific embodiment of the present invention;

17 is the photoelectric conversion current efficiency of the device using complex 31 in the specific embodiment of the present invention;

Fig. 18 is the power efficiency of photoelectric conversion of the device using complex 31 in the specific embodiment of the present invention;

FIG. 19 is a graph showing the luminescence stability of devices using complexes 31 and 46 in an embodiment of the present invention;

FIG. 20 is an excited state electron distribution diagram of the complex 31 in the specific embodiment of the present invention.

Detailed ways

The present invention is further illustrated by the following examples and comparative examples. These examples are only used to illustrate the present invention, and the present invention is not limited to the following examples. Any modification or equivalent replacement to the technical solution of the present invention without departing from the scope of the technical solution of the present invention should be included in the protection scope of the present invention. The present invention may be understood more readily by reference to the following detailed description and the examples contained therein.

compound

In some specific embodiments of the present invention, a metal platinum coordination compound (referred to as a divalent platinum complex) having a structure as shown in formula I is provided:

wherein R ^a , R ^b , R ^c , R ^d and R ^f are each independently mono- or di-substituted, and R ^a , R ^b , R ^c , R ^d and R ^f are each independently selected from monoatomic substituents or polyatomic substituents; the monoatomic substituents include hydrogen atoms, isotopic atoms or halogen atoms thereof; the polyatomic substituents include alkyl, aryl-substituted alkyl, fluorine-substituted alkyl, aryl, alkane aryl substituted aryl, aryl substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, hydroxyl, mercapto, nitro, cyano, isocyano, sulfinyl , sulfonyl, carboxyl, hydrazine, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, amido, alkane Oxycarbonylamino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramido, silyl, polymer groups, or the aforementioned substituents containing isotopic atoms; R ^e Selected from an alkyl group containing 2 or more carbons, an aryl-substituted alkyl group, a fluorine-substituted alkyl group, an aryl group, an alkyl-substituted aryl group, an aryl-substituted aryl group, or a cycloalkyl group.

In some embodiments of the invention, ^Ra , ^Rb , ^Rc , ^Rd and ^Rf are each independently selected from deuterium, tritium, fluorine, chlorine, bromine or iodine atoms.

In some embodiments of the invention, R ^a , R ^b , R ^c , R ^d and R ^f are each independently selected from hydrogen atoms, methyl, benzyl, diphenylmethyl, triphenylmethyl ; ethyl, 2-phenylethyl, 2,2-phenylethyl, 2,2,2-trifluoroethyl; propyl, isopropyl, 3,3,3-trifluoropropyl, 1 ,1,1,3,3,3-hexafluoro-2-propyl; butyl, isobutyl, hexafluoroisobutyl, tert-butyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , cycloheptyl; phenyl, 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-ethylbenzene phenyl, 4-tert-butylphenyl, 2,3-dimethylphenyl, 2,3-diethylphenyl, 2,3-diisopropylphenyl, 2,3-diisobutylbenzene base, 2,3-dicyclohexylphenyl, 2,3-dicyclopropylphenyl, 2,3-dicyclobutylphenyl, 2,3-dicyclopentylphenyl, 2,4-dicyclopentylphenyl Methylphenyl, 2,4-diethylphenyl, 2,4-diisopropylphenyl, 2,4-diisobutylphenyl, 2,4-dicyclohexylphenyl, 2,4 -Dicyclopropylphenyl, 2,4-dicyclobutylphenyl, 2,4-dicyclopentylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,6-diisobutylphenyl, 2,6-dicyclohexylphenyl, 2,6-dicyclopropylphenyl, 2,6-dicyclobutane phenyl, 2,6-dicyclopentylphenyl, 3,5-dimethylphenyl, 3,5-diethylphenyl, 3,5-diisopropylphenyl, 3,5- Diisobutylphenyl, 3,5-dicyclohexylphenyl, 3,5-dicyclopropylphenyl, 3,5-dicyclobutylphenyl, 3,5-dicyclopentylphenyl, 2,3,5,6-Tetramethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl , 2,4,6-triisobutylphenyl, 2,4,6-tricyclohexylphenyl, 2,4,6-tricyclopropylphenyl, 2,4,6-tricyclobutylbenzene base, 2,4,6-tricyclopentylphenyl.

In some specific embodiments of the present invention, ^Re is selected from benzyl, diphenylmethyl, triphenylmethyl; ethyl, 2-phenylethyl, 2,2-phenylethyl, 2 ,2,2-trifluoroethyl; propyl, isopropyl, 3,3,3-trifluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl; butyl , isobutyl, hexafluoroisobutyl, tert-butyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl; phenyl, 2-methylphenyl, 2-isopropylbenzene phenyl, 2-ethylphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 2,3-dimethylphenyl, 2 ,3-diethylphenyl, 2,3-diisopropylphenyl, 2,3-diisobutylphenyl, 2,3-dicyclohexylphenyl, 2,3-dicyclopropylbenzene base, 2,3-dicyclobutylphenyl, 2,3-dicyclopentylphenyl, 2,4-dimethylphenyl, 2,4-diethylphenyl, 2,4-diiso Propylphenyl, 2,4-diisobutylphenyl, 2,4-dicyclohexylphenyl, 2,4-dicyclopropylphenyl, 2,4-dicyclobutylphenyl, 2, 4-Dicyclopentylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,6-diisobutylphenyl , 2,6-dicyclohexylphenyl, 2,6-dicyclopropylphenyl, 2,6-dicyclobutylphenyl, 2,6-dicyclopentylphenyl, 3,5-dimethylphenyl phenyl, 3,5-diethylphenyl, 3,5-diisopropylphenyl, 3,5-diisobutylphenyl, 3,5-dicyclohexylphenyl, 3,5- Dicyclopropylphenyl, 3,5-dicyclobutylphenyl, 3,5-dicyclopentylphenyl, 2,3,5,6-tetramethylphenyl, 2,4,6-tris Methylphenyl, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl, 2,4,6-triisobutylphenyl, 2,4,6-triisopropylphenyl Cyclohexylphenyl, 2,4,6-tricyclopropylphenyl, 2,4,6-tricyclobutylphenyl, 2,4,6-tricyclopentylphenyl.

In some embodiments of the invention, R ^a , R ^b , R ^c , R ^d and R ^f are each independently selected from deuterium, -CDH ₂ , -CD ₂ H, -CD ₃ , -CDR ¹ R ² , -CD ₂ R ¹ , wherein R ¹ and R ² are each independently selected from alkyl, aryl-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, cycloalkyl, cyclic Alkenyl, heteroaryl, alkenyl, alkynyl, amino, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester, alkoxy Carbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramido, silyl, polymer groups.

In some embodiments of the present invention, R ^e is selected from -CDR ³ R ⁴ , -CD ₂ R ³ , wherein R ³ and R ⁴ are each independently selected from alkyl, aryl-substituted alkyl, aryl , alkyl substituted aryl, aryl substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diaryl amino, alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio, urea group, phosphoramide group, silyl group, polymer group.

In some specific embodiments of the present invention, the provided divalent platinum complex has the structure shown in formula II or formula III:

In Structural Formula II, in one aspect, R ^a is a substituent other than a hydrogen atom, and the immobilization site is at the para position of the pyridine N. On the other hand, R ^b , R ^c , R ^d and R ^f may represent mono-substituted substituents or di-substituted substituents R ¹ and R ² , the di-substituted substituents R ¹ and R ² being independently deuterium, CDH ₂ , CD ₂ H, CD ₃ , CDR ¹ R ² , CD ₂ R ¹ , R ¹ and R ² are each independently selected from alkyl, aryl substituted alkyl, fluorine substituted alkyl, aryl, alkyl Substituted aryl, aryl substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, Alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphorus Amide group, silyl group, polymer group.

Each R ^e is an independent substituent with more than 2 carbons, which can be alkyl, aryl-substituted alkyl, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, Cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester group, alkoxycarbonyl group, amido group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, urea group, phosphoramido group, silyl group, polymer group.

In structural formula III, in one aspect, R ^d is a substituent other than a hydrogen atom, and the anchoring site is at the para position of the benzene ring of Pt-C. On the other hand, R ^b , R ^c , ^Ra and R ^f may represent mono-substituted substituents or di-substituted substituents R ¹ and R ² , the di-substituted substituents R ¹ and R ² being independently deuterium, CDH ₂ , CD ₂ H, CD ₃ , CDR ¹ R ² , CD ₂ R ¹ , R ¹ and R ² are each independently selected from alkyl, aryl substituted alkyl, fluorine substituted alkyl, aryl, alkyl Substituted aryl, aryl substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, Alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphorus Amide group, silyl group, polymer group.

Each R ^e is an independent substituent with more than 2 carbons, which can be alkyl, aryl-substituted alkyl, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, Cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester group, alkoxycarbonyl group, amido group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, urea group, phosphoramido group, silyl group, polymer group.

In some specific embodiments of the present invention, R ^b , R ^c and R ^f are hydrogen atoms; R ^a and R ^d are each independently selected from methyl or hydrogen atoms; R ^e is selected from isopropyl, isobutyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl.

In other specific embodiments of the present invention, the provided divalent platinum complex has a structure selected from one of the following complexes 1-75:

In the following specific embodiments of the present invention, the complex 16, the complex 18, the complex 21, the complex 31, the complex 46 and the complex 61 will be taken as examples to specifically illustrate the divalent platinum complexes provided by the present invention. The synthesis method, properties and performance of the compound as a luminescent material.

Among them, complexes 16 and 31 represent that the substituent Re is a large group alkyl group; complex 18 represents that there is a substituent at the highest occupied orbital (HOMO) end of the molecule, representing structural formula II; complex 21 represents that in the molecule The lowest unoccupied orbital (LUMO) end is substituted with a substituent, representing structure III; structures II and III also have the material properties of formula I, and are a case of the complex represented by formula I.

compound synthesis

Various methods of preparing the compounds provided herein are exemplary. These methods are intended to illustrate various preparation methods, but are not intended to be limited to any particular method, and temperatures, catalysts, concentrations, reactant compositions, and other process conditions may vary.

¹ H NMR (hydrogen nuclear magnetic resonance) and ¹³ C NMR (carbon nuclear magnetic resonance) spectra were recorded at 300, 400 or 500 MHz by a Varian liquid-state nuclear magnetic resonance apparatus in _CDCl or _DMSO -d solutions, while chemical shifts were in residual protons The solvent is used as the benchmark. If CDCl ₃ was used as solvent, ^1H NMR (Hydrogen Nuclear Magnetic Resonance) spectra were recorded using tetramethylsilane (δ=0.00 ppm) as internal reference; ¹³ C was recorded using CDCl ₃ (δ=77.00 ppm) as internal reference NMR (carbon nuclear magnetic resonance) spectroscopy. If DMSO-d ₆ was used as solvent, ¹ H NMR (Hydrogen Nuclear Magnetic Resonance) spectra were recorded using residual H ₂ O (δ=3.33 ppm) as internal reference; DMSO-d ₆ (δ=39.52 ppm) was used as internal reference ¹³ C NMR (Carbon Nuclear Magnetic Resonance) spectra were recently recorded. The following abbreviations are used to illustrate the variety of ¹ H NMR (Hydrogen Nuclear Magnetic Resonance): s=singlet, d=doublet, t=triplet, q=quadlet, p=pentet, m=many Linear, br = width.

General synthetic method:

The complex provided by the present invention can be synthesized by the following general route, and the specific steps are the coupling reaction of the fragment, the cyclization reaction of the phenylimidazole ring and the metal coordination reaction.

Wherein, the definitions of R ^a , R ^b , R ^c , R ^d , ^Re and R ^f are the same as those of formula I.

Example 1

Complex 16 and its preparation

Synthesis of 2-bromo-9-(2-pyridyl)carbazole:

2-Bromocarbazole 0001 (3.69g, 15mmol), 2-bromopyridine 0002 (1.57mL, 16.5mmol), cuprous iodide (0.3mmL, 0.02equiv), 1-Methylimidazole (0.3 mmol, 1.2 equiv), t-BuOLi (18 mmol, 1.2 equiv) and toluene (50 mL), the resulting mixture was sparged with nitrogen for 10 minutes and then heated to 120°C and stirred for 8 hours. Cool to room temperature, add water to quench the reaction, extract with ethyl acetate, combine the organic phases, wash with an appropriate amount of saturated aqueous sodium chloride solution, add anhydrous sodium sulfate and dry. The solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography, the eluent was petroleum ether:ethyl acetate=25:1, to obtain a white solid with a yield of 93%.

Synthesis of 2-(3-amino-phenolyl)-9-(2-pyridyl)carbazole 0005:

To a 25ml Shrek tube add 2-bromo-9-(2-pyridyl)carbazole 0003 (1 equiv), 3-amino-phenol 0004 (1.2 equiv), cuprous iodide (10%), L-pro Amino acid (L-Pro, 20%), cesium carbonate (2equiv) and dimethyl sulfoxide (0.5M). The resulting mixture was sparged with nitrogen for 10 minutes and stirred at 120°C for 3 days. After cooling, water and ethyl acetate (EA) were added, and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and the organic phase was dried over anhydrous Na ₂ SO ₄ . Using PE:EA=8:1 as the eluent, the obtained solution was purified by silica gel chromatography to obtain the target product 0005 (brown viscous liquid, yield 75%).

Synthesis of 2-Bromo-N-isopropyl-aniline 1102:

15 ml of acetone and 75 ml of acetic acid were added to a solution of 8 g of o-bromoaniline 1101 in 150 ml of dichloromethane. 6 ml of borane dimethyl sulfide solution was added at 0°C, followed by stirring at room temperature overnight. After the reaction was completed, 25wt% ammonia solution was added to adjust the pH to 8. After adding 50 ml of water, it was extracted three times with dichloromethane. The organic phase was collected and dried with anhydrous sodium sulfate, and the crude product of compound 1102 was obtained by spin drying and used directly in the next step (yellow oil, yield 95%).

Synthesis of phenylenediamine derivative 1103:

To a sealed tube in the glove box add 2-bromo-N-(isopropyl)-aniline 1102 (1equiv), 2-(3-amino-phenolyl)-9-(2-pyridyl)carbazole 0005 ( 1.1 equiv), palladium acetate (5%), J-phos (2-(dicyclohexylphosphino)biphenyl, 5%), sodium tert-butoxide (1.5 equiv) and toluene (0.2M). After letting the mixture bubble for 15 minutes, the mixture was heated at 130°C for 18 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, and the organic phases were combined, washed with brine, and dried over anhydrous Na ₂ SO ₄ . Using PE:EA=6:1 as the eluent, the obtained solution was purified by silica gel chromatography, and the eluent was spin-dried to obtain the target product 1103 (yellow viscous liquid, yield 80%). ¹ H NMR (300MHz, DMSO) δ 8.67 (d, J=3.6Hz, 1H), 8.20-8.16 (m, 2H), 8.06 (td, J=7.8, 1.9Hz, 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 ⁺ ]

Synthesis of Carbene Hexafluorophosphate 1104:

To a sealed tube was added the phenylenediamine derivative 1103 (1 equiv), ammonium hexafluorophosphate (1.1 equiv) and triethyl orthoformate (0.5 M). Heated at 120°C overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to obtain product 1104 (yellow solid, yield 60%).

Synthesis of complex 16:

Carbene hexafluorophosphate 1104 (1 equiv), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl ₂ , 0.9 equiv), sodium acetate (1.05 equiv), and THF (0.5M). Heated at 120°C for 3 days. After cooling to room temperature, it was spin-dried. Using DCM:PE=4:1 as eluent, the obtained solution was purified by silica gel chromatography to obtain the target product: complex 16 (bright yellow powder, yield 38%)

¹ H-NMR (300MHz, DMSO) δ9.52 (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 ⁺ ]

Example 2

Complex 18 and its preparation

Synthesis of 2-(3-methyl-5-amino-phenolyl)-9-(2-pyridyl)carbazole 0007:

To a 25ml Shrek tube, add 2-bromo-9-(2-pyridyl)carbazole 0003 (1 equiv), 3-methyl-5-amino-phenol 0006 (1.2 equiv), cuprous iodide (10% ), L-proline (L-Pro, 20%), cesium carbonate (2equiv) and dimethylsulfoxide (0.5M). The resulting mixture was sparged with nitrogen for 10 minutes and stirred at 120°C for 3 days. After cooling, water and ethyl acetate (EA) were added, and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and the organic phase was dried over anhydrous Na ₂ SO ₄ . Using PE:EA=8:1 as the eluent, the obtained solution was purified by silica gel chromatography to obtain the target product 0007 (brown viscous liquid, yield 75%).

Synthesis of 2-Bromo-N-isopropyl-aniline 1102:

15 ml of acetone and 75 ml of acetic acid were added to a solution of 8 g of o-bromoaniline 1101 in 150 ml of dichloromethane. 6 ml of borane dimethyl sulfide solution was added at 0°C, followed by stirring at room temperature overnight. After the reaction was completed, 25wt% ammonia solution was added to adjust the pH to 8. After adding 50 ml of water, it was extracted three times with dichloromethane. The organic phase was collected and dried with anhydrous sodium sulfate, and the crude product of compound 1102 was obtained by spin drying and used directly in the next step (yellow oil, yield 95%).

Synthesis of phenylenediamine derivative 2103:

To a sealed tube in the glove box, add 2-bromo-N-(isopropyl)-aniline 1102 (1equiv), 2-(3-methyl-amino-phenolyl)-9-(2-pyridyl)carbohydrate oxazole 0007 (1.1 equiv), palladium acetate (5%), J-phos (2-(dicyclohexylphosphino)biphenyl, 5%), sodium tert-butoxide (1.5 equiv) and toluene (0.2M). After letting the mixture bubble for 15 minutes, the mixture was heated at 130°C for 18 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, and the organic phases were combined, washed with brine, and dried over anhydrous Na ₂ SO ₄ . Using PE:EA=6:1 as the eluent, the obtained solution was purified by silica gel chromatography, and the eluent was spin-dried to obtain the target product 2103 (yellow viscous liquid, yield 80%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.72-8.69 (m, 1H), 8.07 (d, J=8.00 Hz, 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).

Synthesis of Carbene Hexafluorophosphate 2104:

To a sealed tube was added the phenylenediamine derivative 2103 (1 equiv), ammonium hexafluorophosphate (1.1 equiv) and triethyl orthoformate (0.5 M). Heated at 120°C overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to obtain product 2104 (yellow solid, yield 60%).

Synthesis of complex 18:

Carbene hexafluorophosphate 2104 (1 equiv), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl ₂ , 0.9 equiv), sodium acetate (1.05 equiv), and THF (0.5M). Heated at 120°C for 3 days. After cooling to room temperature, it was spin-dried. Using DCM:PE=4:1 as eluent, the obtained solution was purified by silica gel chromatography to obtain the target product: complex 18 (bright yellow powder, yield 38%). ¹ H 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 ⁺ ]

Implementation Column 3

Complex 21 and its preparation

Synthesis of 2-bromo-9-(4-methyl-2-pyridyl)carbazole:

2-Bromocarbazole 0001 (1 eqiv, 15 mmol), 2-bromo-4-picoline 0008 (1.1 eqiv 16.5 mmol), and cuprous iodide (0.3 mmL, 0.02 mmol) were sequentially added to a 48 mL sealed tube with a magnetic rotor. equiv), 1-methylimidazole (0.3 mmol, 1.2 equiv), t-BuOLi (18 mmol, 1.2 equiv) and toluene (50 mL), the resulting mixture was sparged with nitrogen for 10 minutes and heated to 120°C with stirring for 8 hours. Cool to room temperature, add water to quench the reaction, extract with ethyl acetate, combine the organic phases, wash with an appropriate amount of saturated aqueous sodium chloride solution, add anhydrous sodium sulfate and dry. The solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography, the eluent was petroleum ether:ethyl acetate=25:1, to obtain a white solid with a yield of 93%.

Synthesis of 2-(3-amino-phenolyl)-9-(4-methyl-2-pyridyl)carbazole 0010:

To a 25ml Shrek tube add 2-bromo-9-(4-methyl-2-pyridyl)carbazole 0009 (1 equiv), 3-amino-phenol 0004 (1.2 equiv), cuprous iodide (10% ), L-proline (L-Pro, 20%), cesium carbonate (2equiv) and dimethylsulfoxide (0.5M). The resulting mixture was sparged with nitrogen for 10 minutes and stirred at 120°C for 3 days. After cooling, water and ethyl acetate (EA) were added, and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and the organic phase was dried over anhydrous Na ₂ SO ₄ . Using PE:EA=8:1 as the eluent, the obtained solution was purified by silica gel chromatography to obtain the target product 0010 (brown viscous liquid, yield 75%).

Synthesis of phenylenediamine derivative 3103:

To a sealed tube in the glove box, add 2-bromo-N-(isopropyl)-aniline 1102 (1equiv), 2-(3-amino-phenolyl)-9-(4-methyl-2-pyridyl) ) carbazole 0010 (1.1 equiv), palladium acetate (5%), J-phos (2-(dicyclohexylphosphino)biphenyl, 5%), sodium tert-butoxide (1.5 equiv) and toluene (0.2M) . After letting the mixture bubble for 15 minutes, the mixture was heated at 130°C for 18 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, and the organic phases were combined, washed with brine, and dried over anhydrous Na ₂ SO ₄ . Using PE:EA=6:1 as the eluent, the obtained solution was purified by silica gel chromatography, and the eluent was spin-dried to obtain the target product 3103 (yellow viscous liquid, yield 80%). ¹ H NMR (500MHz, CDCl ₃ ) δ 8.55 (d, J=5.00 Hz, 1H), 8.07 (d, J=8.1 Hz, 1H), 8.04 (d, J=12.60 Hz, 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).

Synthesis of Carbene Hexafluorophosphate 3104:

To a sealed tube was added the phenylenediamine derivative 3103 (1 equiv), ammonium hexafluorophosphate (1.1 equiv) and triethyl orthoformate (0.5 M). Heated at 120°C overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to obtain product 3104 (yellow solid, yield 60%).

Synthesis of complex 21:

Carbene hexafluorophosphate 3104 (1 equiv), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl ₂ , 0.9 equiv), sodium acetate (1.05 equiv) and THF (0.5M). Heated at 120°C for 3 days. After cooling to room temperature, it was spin-dried. Using DCM:PE=4:1 as eluent, the obtained solution was purified by silica gel chromatography to obtain the target product: complex 21 (bright yellow powder, yield 38%). ¹ H NMR(500MHz,DMSO)δ9.39(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 ⁺ ]

Example 4

Synthesis of complex 31

Synthesis of 2-bromo-N-isobutyl-aniline 4102:

15 ml of acetone and 75 ml of acetic acid were added to a solution of 8 g of o-bromoaniline 1101 in 150 ml of dichloromethane. 6 ml of borane dimethyl sulfide solution was added at 0°C, followed by stirring at room temperature overnight. After the reaction was completed, 25wt% ammonia solution was added to adjust the pH to 8. After adding 50 ml of water, it was extracted three times with dichloromethane. The organic phase was collected and dried with anhydrous sodium sulfate, and the crude product of compound 4102 was obtained by spin-drying and used directly in the next step (yellow oil, yield 96%).

Synthesis of phenylenediamine derivative 4103:

To a sealed tube in the glove box add 2-bromo-N-(isopropyl)-aniline 4102 (1equiv), 2-(3-amino-phenolyl)-9-(2-pyridyl)carbazole 0005 ( 1.1 equiv), palladium acetate (5%), J-phos (2-(dicyclohexylphosphino)biphenyl, 5%), sodium tert-butoxide (1.5 equiv) and toluene (0.2M). After letting the mixture bubble for 15 minutes, the mixture was heated at 130°C for 18 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, and the organic phases were combined, washed with brine, and dried over anhydrous Na ₂ SO ₄ . Using PE:EA=6:1 as the eluent, the obtained solution was purified by silica gel chromatography, and the eluent was spin-dried to obtain the target product 4103 (yellow viscous liquid, yield 84%). ¹ H NMR (300MHz, DMSO) δ 8.67 (dd, J=4.80, 1.20 Hz, 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 ⁺ ]

Synthesis of Carbene Hexafluorophosphate 4104:

To a sealed tube was added the phenylenediamine derivative 4103 (1 equiv), ammonium hexafluorophosphate (1.1 equiv) and triethyl orthoformate (0.5 M). Heated at 120°C overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to obtain product 4104 (yellow solid, yield 67%).

Synthesis of complex 31:

Carbene hexafluorophosphate 4104 (1 equiv), dichloro(1,5-cyclooctadiene) platinum(II) (Pt(COD)Cl ₂ , 0.9 equiv), sodium acetate (1.05 equiv), and THF (0.5M). Heated at 120°C for 3 days. After cooling to room temperature, it was spin-dried. Using DCM:PE=4:1 as eluent, the obtained solution was purified by silica gel chromatography to obtain the target product: complex 31 (bright yellow powder, yield 39%). ¹ H 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=7.50 Hz,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 ⁺ ]

Example 5

Synthesis of complex 46:

Synthesis of phenylenediamine derivative 5102:

To a sealed tube in the glove box add o-dibromobenzene 5101 (1 equiv), 2-(3-amino-phenolyl)-9-(2-pyridyl)carbazole 0005 (1.1 equiv), palladium acetate (5% ), J-phos (2-(dicyclohexylphosphino)biphenyl, 5%), sodium tert-butoxide (1.5 equiv) and toluene (0.2M). After letting the mixture bubble for 15 minutes, the mixture was heated at 130°C for 18 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, and the organic phases were combined, washed with brine, and dried over anhydrous Na ₂ SO ₄ . Using PE:EA=6:1 as the eluent, the obtained solution was purified by silica gel chromatography, and the eluent was spin-dried to obtain the target product 5102 (yellow viscous liquid, yield 78%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.70 (d, J=3.50 Hz, 1H), 8.07 (dd, J=8.5, 4.0 Hz, 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 ⁺ ]

Synthesis of phenylenediamine derivative 5104:

To a sealed tube in the glove box add 2,4,6-trimethyl-aniline 5103 (1equiv), 2-(3-(N-2-bromophenyl)-phenolyl)-9-(2-pyridine yl)carbazole 5102 (1.1 equiv), palladium acetate (5%), J-phos (2-(dicyclohexylphosphino)biphenyl, 5%), sodium tert-butoxide (1.5 equiv) and toluene (0.2 M ). After letting the mixture bubble for 15 minutes, the mixture was heated at 130°C for 18 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, and the organic phases were combined, washed with brine, and dried over anhydrous Na ₂ SO ₄ . Using PE:EA=6:1 as the eluent, the obtained solution was purified by silica gel chromatography, and the eluent was spin-dried to obtain the target product 5104 (yellow viscous liquid, yield 87%). ¹ H 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 ⁺ ]

Synthesis of Carbene Hexafluorophosphate 5105:

To a sealed tube was added the phenylenediamine derivative 5104 (1 equiv), ammonium hexafluorophosphate (1.1 equiv) and triethyl orthoformate (0.5 M). Heated at 120°C overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to obtain product 5105 (yellow solid, yield 61%).

Synthesis of complex 46:

Carbene hexafluorophosphate 5105 (1 equiv), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl ₂ , 0.9 equiv), sodium acetate (1.05 equiv) and THF (0.5M). Heated at 120°C for 3 days. After cooling to room temperature, it was spin-dried. Using DCM:PE=4:1 as eluent, the obtained solution was purified by silica gel chromatography to obtain the target product: complex 46 (bright yellow powder, yield 32%). ¹ H NMR(300MHz, DMSO)δ8.63(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 ⁺ ]

Example 6

Complex 61 and its preparation

Synthesis of phenylenediamine derivative 6102:

To a sealed tube in the glove box add 2,6-diisopropyl-aniline 6101 (1equiv), 2-(3-(N-2-bromophenyl)-phenolyl)-9-(2-pyridine yl)carbazole 5102 (1.1 equiv), palladium acetate (5%), J-phos (2-(dicyclohexylphosphino)biphenyl, 5%), sodium tert-butoxide (1.5 equiv) and toluene (0.2 M ). After letting the mixture bubble for 15 minutes, the mixture was heated at 130°C for 18 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, and the organic phases were combined, washed with brine, and dried over anhydrous Na ₂ SO ₄ . Using PE:EA=6:1 as the eluent, the obtained solution was purified by silica gel chromatography, and the eluent was spin-dried to obtain the target product 6102 (yellow viscous liquid, yield 84%). ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.68 (d, J=4.80 Hz, 1H), 8.06 (t, J=8.15 Hz, 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 ⁺ ]

Synthesis of Carbene Hexafluorophosphate 6103:

To a sealed tube was added the phenylenediamine derivative 6102 (1 equiv), ammonium hexafluorophosphate (1.1 equiv) and triethyl orthoformate (0.5 M). Heated at 120°C overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to obtain product 6103 (yellow solid, yield 56%).

Synthesis of complex 61:

Carbene hexafluorophosphate 6103 (1 equiv), dichloro(1,5-cyclooctadiene) platinum(II) (Pt(COD)Cl ₂ , 0.9 equiv), sodium acetate (1.05 equiv), and THF (0.5M). Heated at 120°C for 3 days. After cooling to room temperature, it was spin-dried. Using DCM:PE=4:1 as eluent, the obtained solution was purified by silica gel chromatography to obtain the target product: complex 61 (bright yellow powder, yield 33%). ¹ H 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 ⁺ ]

Characterization of Compounds

Embodiments of the present invention also provide applications of the above-mentioned divalent platinum complexes as electroluminescent materials or photoluminescent materials.

Optionally, the divalent platinum complex is a blue light emitting material or a phosphorescent light emitting material. The blue light wavelength peak of the divalent platinum complex provided by the embodiment of the present invention is in the range of 450-470 nm, and further, the blue light spectrum of the divalent platinum complex provided by the embodiment of the present invention exceeds 50% at 450 nm. ~490nm range.

The emission spectrum of the divalent platinum complex of the present invention shows that the triplet energy gap is almost the same when deuterium atoms are added to the ligand.

Representative data for the color purity of the emitters can be obtained from emission spectra of thin films prepared using a 5% solution of PMMA (polymethyl methacrylate) in dichloromethane. Table 1 shows the emission spectrum data of the complexes. In Table 1 below, λ is the peak wavelength, FWHM is the half-peak width, 450-700nm is the ratio of the integral of the emission spectrum in the 450-500nm interval, and CIE(x,y) is the chromaticity coordinate parameter according to the International Commission on Illumination. . The peak wavelengths of the complexes 16, 18, 21, 31, 46, and 61 prepared in the examples of the present invention are between 455-456, and the half-peak width is between 19-28 nm. The spectral proportion within the range of 450-500nm in the blue light emitting region that is in line with visual health reaches more than 70%. Moreover, the four example divalent platinum complexes are all within the deep blue light emission range (x<0.15, y<0.15), among which complexes 16, 21, 31, 46 and 61 reach the standard of pure blue light materials (X=0.14, Y=0.10); the characteristics of low energy and narrow spectrum ensure that this divalent platinum complex becomes an extremely excellent blue light material.

Table 1 Emission Spectral Data

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, the description of the relevant drawings is as follows:

Figures 1-3 show the luminescence spectra of the divalent platinum complexes 16, 31 and 46 in solution and film respectively; under the excitation of 340nm ultraviolet light, the luminescence wavelengths of the three complexes in dichloromethane solution are at Between 450-500nm, the emission wavelength in polymethyl methacrylate (PMMA) is between 450-480nm, the wavelength of all complexes is in the deep blue light region, and the half-peak width of the spectrum is narrow, indicating that this series of complexes It is a good blue light-emitting material. Among them, Figure 1 shows that the emission peak of the emission spectrum of the divalent platinum complex 16 in the PMMA film is 458 nm, the half-peak width is 28 nm, and the number of photons in the effective blue light interval exceeds 75%.

Figure 4 shows the ultraviolet-visible absorption spectra of the above-mentioned divalent platinum complexes 16, 31 and 61 in dichloromethane solution. According to the absorption spectra, it can be known that the absorption spectra are very strongly absorbed in the long wavelength region 280-420 nm, This absorption region is distinct from the ligand precursor. Among them, 280-330 nm can be assigned to the π-π* transition centered on carbazole in the complex. The absorption peak after 330nm can be attributed to the valence state transfer transition (MLCT) transition between the central metal ion and the ligand. This part of the transition is very strong on this divalent platinum complex, the kurtosis can reach half of the ligand absorption kurtosis, and the extinction coefficient can reach 2.5×10 ^-4 ·M ^-1 ·cm ^-1 . This shows that the energy absorption of such molecules is very efficient and can be used as the preferred molecular structure of dopant material molecules. The wavelength below 300nm is the ππ* transition allowed by the spin of the cyclic ligand, and the wavelength 300nm-340nm is the ππ* transition of the carbazole ligand part; the absorption above 340nm comes from the dπ* transition of the transfer state of the metal to the ligand. . Among them, the absorption peak between 300-400 nm is related to the ¹ LC ( ¹ ππ*) transition, and the absorption band is very strong, indicating that this series of compounds has a strong ligand-centered ππ* transition. According to the previously quoted Relevant research results show that this effect is beneficial to obtain blue light emitters with narrow emission spectrum and high color purity. Similarly, the absorption peak between 400-430 is related to the transition of metal-to-ligand charge transfer ( ¹ MLCT), and the absorption band is also very strong, indicating that this series of compounds has a strong ¹ MLCT effect. Theoretically (Yersin, H.; Finkenzeller, WJ Triplet Emitters for Organic Light-Emitting Diodes: Basic Properties; 2008.), this effect can increase the phosphorescence luminescence efficiency of the molecule, and such complex molecules can be used as the preferred molecules for doping materials for phosphorescent devices .

The band gaps and related optical properties of the divalent platinum complexes 16, 18, 21, 31, 46, and 61 provided by the embodiments of the present invention are characterized as follows:

The band gap (E _g ), LUMO and HOMO values of the materials were measured by cyclic voltammetry (CV). The whole test process was carried out on the CHI600D electrochemical workstation (Shanghai Chenhua Instrument Co., Ltd.) in the glove box (Lab2000, Etelux). The Pt column was used as the working electrode, the Ag/AgCl as the reference electrode, and the Pt wire as the auxiliary electrode. Electrode system, the medium used in the test process is 0.1M tetrabutylamine hexafluorophosphate (Bu ₄ NPF ₆ ) solution in dimethylformamide (DMF), and the measured potentials are all ferrocene (Fc) added as internal mark. In the table below, λ is the peak wavelength of the divalent platinum complex dissolved in dichloromethane, FWHM is its half-peak width, and the triplet photon energy (E _T1 ) of the material is calculated from the formula 1240/λ _0→1 (λ _0→1 is the first vibration peak at 77K), and the unit is electron Ford (eV).

Table 2 shows the energy level data of the complexes. It can be seen from the data in Table 2 that the energy levels of the HOMO orbitals of complexes 16, 46 and 61 are lower than those of complex 31, indicating that long-chain alkylation at the N position of benzimidazole can increase the HOMO energy level of the material. The LUMO energy levels of complexes 46 and 61 are lower than those of complexes 16 and 31, indicating that the introduction of aryl substituents on benzimidazoles can increase the LUMO energy levels. The triplet energies of the four divalent platinum complexes are consistent at 2.76 eV, which is mainly related to the structure of the parent nucleus, indicating that the triplet radiative transitions are consistent at low temperature, that is, when the molecular thermal motion is restricted. This also shows that these divalent platinum complexes can control their energy levels and their emission spectra within a small range by introducing substituents, so as to obtain the optimal emission spectrum range.

Table 2 Energy level data

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

Figure 5 shows the frontier orbital distribution of complex 16, the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) distribution. HOMO and LUMO are shown as separate modes, in which the HOMO orbitals are mainly distributed on the six-membered metal ring newly formed by the central atom of phenoxycarbazole and divalent platinum, and the LUMO is more uniformly distributed in pyridine and benzimidazole and platinum. The Pt-C bond coordinated by the central atom, which means that the Pt-C coordination bond in this structure is aromatic, which is beneficial to the stability of the molecular structure.

Figure 6 shows the frontier orbital distribution of complex 46, the HOMO and LUMO are shown to be separated in the same pattern as the main part of complex 16 shown in Figure 5, in which the HOMO orbital is mainly distributed in the phenoxycarbazole and the divalent platinum central atom On the newly formed six-membered metal ring, the main part of LUMO is relatively uniformly distributed in the Pt-C bond coordinated with the central atom of platinum in pyridine and benzimidazole, and the other part of LUMO is distributed in a small amount delocalized to the whole molecule, which shows that by The change of the substituent R ^e can control the excited state orbital distribution of the complex molecule, so as to obtain a more stable molecular structure of the complex in the process of photophysical conversion.

Figure 7 depicts the triplet excited state charge and hole distribution of complex 21, combined with the frontier orbital of complex 16, indicating that there are multiple groups of high-energy orbitals participating in the first excited state of the triplet state, forming in the singlet state Different electron distribution, the process of charge delocalization formed in the process of singlet to triplet transition is called delocalized single → triplet spin transition (Delocalized Spin Transition, DST) mechanism, obviously, has The representative complex 16 has a DST mechanism transition process, which is the transfer of excited state charges from the pyridine end to the carbazole and N-phenylbenzimidazole fragment structures, resulting in the formation of more ³ LC ( ³ ππ*) transition components, resulting in a small change in the excited state structure and ultimately a narrow vibrationally confined luminescence spectrum.

In addition, the description of the related drawings of compound structure characterization is as follows:

FIG. 8 is the ¹ H nuclear magnetic spectrum of the single molecule of complex 16, which shows that the complex can exist independently and stably and can be separated, purified and characterized by hydrogen spectrum. From the nuclear magnetic spectrum, in addition to the stable structural characterization of the divalent platinum complex, the divalent platinum complex does not show the signal of the aggregation form, indicating that the divalent platinum complex molecule in the solution state is a single monovalent platinum complex. The state of separation of molecules exists.

FIG. 9 is the ¹ H NMR spectrum of the single molecule of complex 31, which shows that the complex can exist independently and stably and can be separated, purified and characterized by hydrogen spectrum. From the nuclear magnetic spectrum, in addition to the stable structural characterization of the divalent platinum complex, the divalent platinum complex does not show the signal of the aggregation form, indicating that the divalent platinum complex molecule in the solution state is a single monovalent platinum complex. The state of separation of molecules exists.

Figure 10 is the ¹ H nuclear magnetic spectrum of the single molecule of complex 46, which shows that the complex can exist independently and stably and can be separated, purified and characterized by hydrogen spectrum. From the nuclear magnetic spectrum, in addition to the stable structural characterization of the divalent platinum complex, the divalent platinum complex does not show the signal of the aggregation form, indicating that the divalent platinum complex molecule in the solution state is a single monovalent platinum complex. The state of separation of molecules exists.

FIG. 11 is a mass spectrometry characterization diagram of the molecule of complex 31 . The molecular signal of mass spectrometer showed that the M/C peak was 701.18, which was consistent with the molecular ion peak of compound 31, indicating that the structure of the complex was the designed structure.

FIG. 12 is a mass spectrometry characterization of the molecule of complex 46. FIG. The molecular signal of mass spectrometry molecule showed that the M/C peak was 763.09, which was consistent with the molecular ion peak of compound 46, indicating that the structure of the complex was the designed structure.

Fig. 13 is an ultra-high pressure liquid phase purity analysis chart of complex 31 after purification. The purity of the liquid phase was changed to 100%, indicating that the compound can be purified to obtain ultra-high-purity products, which are suitable for process control.

Device example

Device Structure and Performance

Embodiments of the present invention also provide an organic optoelectronic device, which includes a light-emitting layer, and the light-emitting layer includes the above-mentioned divalent platinum complex. Optionally, the divalent platinum complex is a light-emitting material, a host material or a guest material in the light-emitting layer of the organic optoelectronic device.

Figure 14 shows a cross-sectional view of an OLED light-emitting device 1000 comprising a divalent platinum complex disclosed herein. The OLED device 1000 includes a substrate 1002 , an anode layer 1004 , a hole transport layer 1006 , an emission layer 1008 , an electron transport layer 1010 , and a metal cathode layer 1012 . Anode 1004 is typically a transparent material such as indium tin oxide. The light-emitting layer 1008 may be a light-emitting material including an emitter and a host. The EIL refers to the electron injection layer, which can be regarded as a part of the electron transport layer 1010 . The HIL is a hole injection layer and can be considered a part of the hole transport layer 1006 . CPL is the cathode capping layer. The complex 101 disclosed herein is used in the 1008 light emitting layer as a blue light emitting dopant material. When the divalent platinum complex was used as a dopant material in an OLED device, the device was prepared by spin coating, and the structure was ITO/PEDOT:PSS(70nm)/host material:divalent platinum complex (1000-x:x, 40nm)/DPEPO(10nm)/TmPyPB(50nm)/Liq(1nm)/Al(100nm).

In the above specific embodiment, the light-emitting layer 1008 may contain one or more divalent platinum complexes provided by the present invention, optionally together with a host material. The ETL layer 1010 and HTL 1006 may also contain one or more divalent platinum complexes and another injection layer in proximity to the electrodes. Materials for the injection layer may include EIL (electron injection layer), HIL (hole injection layer), and CPL (cathode capping layer), which may be in the form of a single layer or dispersed in an electron or hole transport material. The host material may be any suitable host material known in the art. The light-emitting color of the OLED is determined by the light-emitting energy (optical energy gap) of the light-emitting layer 1008 material, and the light-emitting energy ( optical energy gap). The hole transport material in HTL layer 1006 and the electron transport material in ETL layer 1010 may comprise any suitable hole transporter known in the art.

The divalent platinum complex provided by the embodiment of the present invention can exhibit phosphorescence. Phosphorescent OLEDs (i.e. OLEDs with phosphorescent emitters) generally have higher device efficiencies than other OLEDs such as fluorescent OLEDs. Light emitting devices based on electrophosphorescent emitters are described in Nature 1998 395 pp 151-154 and in WO2000/070655 in more detail, since they contain information on The contents of OLEDs, especially fluorescent OLEDs, are hereby incorporated by reference into this application.

Some other device luminous performance related drawings are described as follows:

Figure 15 shows the luminescence spectra of devices using complex 31. The figure illustrates the structure as ITO/PEDOT:PSS(70nm)/2,6-MCPy:complex 31(95:5,40nm)/DPEPO(10nm)/TmPyPB(50nm)/Liq(1nm)/Al(100nm) ) luminescence spectrum of OLEDs. According to the electroluminescence spectrum of the device whose luminescent layer is doped with 5% complex, the luminescence peak is red-shifted by 5 nm relative to its photoluminescence peak in PMMA medium, and the half-peak width is comparable, which maintains the luminescence of the luminescent complex 31 itself. characteristic, and its chromaticity coordinate value is CIE (0.15, 0.18), which indicates that the device emits deep blue light.

Figure 16 shows the electroluminescence spectral range of the device using complex 31, illustrating the structure as ITO/PEDOT:PSS(70nm)/2,6-MCPy:complex 101(95:5,40nm)/DPEPO( Integral normalized plot of the emission spectra of 10 nm)/TmPyPB(50 nm)/Liq(1 nm)/Al(100 nm) OLEDs. According to the normalized integral, only 4.5% of the irritating blue light less than 450nm and 70.2% of the photon energy are above 500nm. According to traditional blue light attribution, blue light photons between 450-500 nm account for 65.7% of all emitted photons.

Figure 17 shows the current efficiency in photoelectric conversion of devices using complex 31, where the device structure is ITO/PEDOT:PSS(70nm)/2,6-MCPy:complex 31(100-x:x,40nm)/ DPEPO(10nm)/TmPyPB(50nm)/Liq(1nm)/Al(100nm) OLED, complex 31 accounts for 2% and 5% in the light-emitting layer material. The photoelectric conversion current efficiency of the complex 31 device has shown a very stable curve. The current roll-off is less than 15% when the current density changes from 0 mA/cm ² to 20 mA/cm ² , and the device with this doped material has a high efficiency, The current efficiencies of 2% and 5% doped devices were 11.5 and 13.4 cd/A at 10 mA/cm ² , respectively, indicating that complex 31 as a blue light-emitting dopant has high-efficiency and stable light-emitting photoconversion properties.

Figure 18 shows the power efficiency in photoelectric conversion of devices using complex 31 with the device structure ITO/PEDOT:PSS(70nm)/2,6-MCPy:complex 31(100-x:x,40nm)/ DPEPO(10nm)/TmPyPB(50nm)/Liq(1nm)/Al(100nm) OLED, complex 31 accounts for 2% and 5% in the light-emitting layer material. where the intercepted power efficiency in the ² % doped device is 10lm/W at 1147cd/m2 brightness, the intercepted power efficiency in the 5% doped device is 12.1lm/W at 1341cd/ ^m2 brightness, and 5 % indicates that the complex 31 as a blue light-emitting dopant has high-efficiency, stable light-emitting photoconversion performance.

Figure 19 shows the luminescence intensity of the devices using complexes 31 and 46 under 0.3mW/cm ² 375nm UV light irradiation with time, indicating that the device can maintain a decay of no more than 5% for 400 minutes under strong luminescence conditions, The spectral attenuation within 6 hours is less than 1%, which indicates that this kind of compound has excellent luminescence stability.

Figure 20 shows the electron distribution of the excited state of complex 31. It can be seen that the negative charge distribution changes during the crossing process from S ₁ → T ₁ , and the distribution on the carbazole fragment increases, thereby increasing the triplet ^3ππ *, this The intrinsic characteristics of excited states with narrow emission spectra are designed for such compounds, which is called the mechanism of delocalized spin transition, and the English name is Delocalized Spin Transition (DST).

Device preparation

The following briefly describes the preparation steps of the OLED light-emitting device with the following structure (prepared by conventional techniques in the art): ITO/PEDOT:PSS(70nm)/MCP:complex 101(95:5,40nm)/DPEPO(10nm)/ TmPyPB(50nm)/Liq(1nm)/Al(100nm).

The crucible containing the OLED organic material and the crucible containing the metal aluminum particles were placed on the positions of the organic evaporation source and the inorganic evaporation source in turn. The chamber was closed, and the initial vacuum and high vacuum steps were performed, so that the vacuum degree of the evaporation inside the OLED evaporation equipment reached 10E ^-7 Torr. OLED evaporation film formation method: turn on the OLED organic evaporation source, preheat the OLED organic material at 100°C, and the preheating time is 15 minutes to ensure that the water vapor in the OLED organic material is further removed. Then, perform rapid heating and heating treatment on the organic material that needs to be evaporated, and open the baffle above the evaporation source until the organic material runs out of the evaporation source of the material, and when the crystal oscillator plate detector detects the evaporation rate, the temperature rises slowly. , the temperature rise range is 1-5℃, until the evaporation rate is stable at 1A/s, open the baffle directly under the mask plate, and conduct OLED film formation. When the computer side observes that the organic film on the ITO substrate reaches the preset film thickness , close the mask baffle plate and the baffle plate just above the evaporation source, and turn off the evaporation source heater of the organic material. The evaporation process of other organic materials and cathode metal materials is as described above. The encapsulation adopts UV epoxy resin for light curing encapsulation. The encapsulated samples were tested for IVL performance, and the IVL equipment was tested with Mc Science M6100.

The performance data of the light-emitting devices prepared above are shown in Table 3.

Table 3 Device luminescence properties

Table 3 shows the comparison of the luminous performance data of each light-emitting device. The electroluminescence wavelength of the light-emitting device is mainly determined by the photoluminescence of the divalent platinum complex itself, and the purity of the photoluminescence spectrum of the divalent platinum complex itself is directly related to the spectral purity of the electroluminescence. Under the same conditions, the efficiency of the light-emitting device is also consistent with the trend of the luminescence quantum efficiency of the divalent platinum complex itself. The electroluminescence spectrum of the divalent platinum complex light-emitting device is compared with that of the photoluminescence device in the thin film. Compared with the photoluminescence spectrum of the thin film, the electroluminescence spectrum of the light-emitting device is slightly red-shifted, but the peak wavelength is still in the blue light region ( 460-470nm), most of the spectrum is also in the blue light range, the calculated chromaticity coordinates show that the light-emitting device belongs to pure blue light-emitting device. Since most of the light is in the blue light range, only a small amount of long-wavelength light needs to be filtered out, indicating that the complex material provided by the embodiment of the present invention can fully meet the chromaticity requirements of pure blue light CIE (0.14, 0.08) in the display .

Those skilled in the art can understand that the above-mentioned embodiments are specific examples for realizing the present invention, and in practical applications, various changes in form and details can be made without departing from the spirit and the spirit of the present invention. scope.

Claims (13)

1. a divalent platinum complex, is characterized in that, has the structure shown in formula I: in, ^Ra , ^Rb , ^Rc , ^Rd , and ^Rf are each independently mono- or disubstituted, and each of ^Ra , ^Rb , ^Rc , ^Rd , and ^{Rf is} independently selected from monoatomic substituents or polyatomic substituents. Atomic substituents; the single-atom substituents include hydrogen atoms, isotopic atoms thereof or halogen atoms; the polyatomic substituents include alkyl groups, aryl-substituted alkyl groups, fluorine-substituted alkyl groups, aryl groups, and alkyl-substituted groups aryl, aryl-substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, hydroxyl, mercapto, nitro, cyano, isocyano, sulfinyl, sulfonyl Acyl, carboxyl, hydrazine, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, amido, alkoxy carbonylamino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramido, silyl, polymer groups, or the aforementioned substituents containing isotopic atoms; R ^e is selected from an alkyl group containing 2 or more carbons, an aryl-substituted alkyl group, a fluorine-substituted alkyl group, an aryl group, an alkyl-substituted aryl group, an aryl-substituted aryl group, or a cycloalkyl group. 2. The divalent platinum complex according to claim 1, wherein R ^a , R ^b , R ^c , R ^d and R ^f are each independently selected from deuterium, tritium, fluorine, chlorine, bromine or iodine atoms . 3. The divalent platinum complex according to claim 1, wherein R ^a , R ^b , R ^c , R ^d and R ^f are independently selected from hydrogen atom, methyl, benzyl, diphenyl ylmethyl, triphenylmethyl; ethyl, 2-phenylethyl, 2,2-phenylethyl, 2,2,2-trifluoroethyl; propyl, isopropyl, 3,3 ,3-trifluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl; butyl, isobutyl, hexafluoroisobutyl, tert-butyl; cyclopropyl, cyclopropyl Butyl, cyclopentyl, cyclohexyl, cycloheptyl; phenyl, 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 4-methylphenyl, 4-isopropyl phenyl, 4-ethylphenyl, 4-tert-butylphenyl, 2,3-dimethylphenyl, 2,3-diethylphenyl, 2,3-diisopropylphenyl, 2,3-diisobutylphenyl, 2,3-dicyclohexylphenyl, 2,3-dicyclopropylphenyl, 2,3-dicyclobutylphenyl, 2,3-dicyclopentyl phenyl, 2,4-dimethylphenyl, 2,4-diethylphenyl, 2,4-diisopropylphenyl, 2,4-diisobutylphenyl, 2,4-diisopropylphenyl Dicyclohexylphenyl, 2,4-dicyclopropylphenyl, 2,4-dicyclobutylphenyl, 2,4-dicyclopentylphenyl, 2,6-dimethylphenyl, 2 ,6-diethylphenyl, 2,6-diisopropylphenyl, 2,6-diisobutylphenyl, 2,6-dicyclohexylphenyl, 2,6-dicyclopropylbenzene base, 2,6-dicyclobutylphenyl, 2,6-dicyclopentylphenyl, 3,5-dimethylphenyl, 3,5-diethylphenyl, 3,5-diiso Propylphenyl, 3,5-diisobutylphenyl, 3,5-dicyclohexylphenyl, 3,5-dicyclopropylphenyl, 3,5-dicyclobutylphenyl, 3, 5-Dicyclopentylphenyl, 2,3,5,6-tetramethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 2,4 ,6-triisopropylphenyl, 2,4,6-triisobutylphenyl, 2,4,6-tricyclohexylphenyl, 2,4,6-tricyclopropylphenyl, 2, 4,6-tricyclobutylphenyl, 2,4,6-tricyclopentylphenyl. 4. The divalent platinum complex according to claim 1, wherein ^Re is selected from benzyl, diphenylmethyl, triphenylmethyl; ethyl, 2-phenylethyl, 2 ,2-phenylethyl, 2,2,2-trifluoroethyl; propyl, isopropyl, 3,3,3-trifluoropropyl, 1,1,1,3,3,3-hexa Fluoro-2-propyl; butyl, isobutyl, hexafluoroisobutyl, tert-butyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl; phenyl, 2-methyl Phenyl, 2-isopropylphenyl, 2-ethylphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 2, 3-dimethylphenyl, 2,3-diethylphenyl, 2,3-diisopropylphenyl, 2,3-diisobutylphenyl, 2,3-dicyclohexylphenyl, 2,3-dicyclopropylphenyl, 2,3-dicyclobutylphenyl, 2,3-dicyclopentylphenyl, 2,4-dimethylphenyl, 2,4-diethyl Phenyl, 2,4-diisopropylphenyl, 2,4-diisobutylphenyl, 2,4-dicyclohexylphenyl, 2,4-dicyclopropylphenyl, 2,4- Dicyclobutylphenyl, 2,4-dicyclopentylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2 ,6-diisobutylphenyl, 2,6-dicyclohexylphenyl, 2,6-dicyclopropylphenyl, 2,6-dicyclobutylphenyl, 2,6-dicyclopentyl Phenyl, 3,5-dimethylphenyl, 3,5-diethylphenyl, 3,5-diisopropylphenyl, 3,5-diisobutylphenyl, 3,5-diisopropylphenyl Cyclohexylphenyl, 3,5-dicyclopropylphenyl, 3,5-dicyclobutylphenyl, 3,5-dicyclopentylphenyl, 2,3,5,6-tetramethylbenzene base, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl, 2,4,6-triisobutylbenzene base, 2,4,6-tricyclohexylphenyl, 2,4,6-tricyclopropylphenyl, 2,4,6-tricyclobutylphenyl, 2,4,6-tricyclopentyl phenyl. 5. The divalent platinum complex according to claim 1, wherein R ^a , R ^b , R ^c , R ^d and R ^f are each independently selected from deuterium, -CDH ₂ , -CD ₂ H, - CD ₃ , -CDR ¹ R ² , -CD ₂ R ¹ , wherein R ¹ and R ² are each independently selected from alkyl, aryl-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, monohydrocarbylamino, dihydrocarbylamino, monoarylamino, diarylamino, alkoxy, aryloxy, Haloalkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramido, silyl, polymer material group. 6. The divalent platinum complex according to claim 1, wherein R ^e is selected from -CDR ³ R ⁴ , -CD ₂ R ³ , wherein R ³ and R ⁴ are each independently selected from alkyl, Aryl-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, monohydrocarbylamino, dihydrocarbyl Amino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoyl, Carbamoyl, alkylthio, urea, phosphoramido, silyl, polymer groups. 7. The divalent platinum complex according to claim 1, wherein the divalent platinum complex has the structure shown in formula II or formula III: in, R in formula II ^or R in ^formula III are each independently selected from alkyl, aryl substituted alkyl, fluoro substituted alkyl, aryl, alkyl substituted aryl, aryl substituted aryl , cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, silyl, polymeric groups, or the aforementioned substituents containing isotopic atoms; The definitions of R ^b , R ^c , R ^d , R ^f and R ^e in formula II are the same as those of formula I; the definitions of R ^a , R ^b , R ^c , R ^f and R ^e in formula III are the same as those of formula I. 8. The divalent platinum complex according to claim 1, wherein R ^b , R ^c and R ^f are hydrogen atoms; R ^a and R ^d are independently selected from methyl or hydrogen atoms; R ^e is selected from From isopropyl, isobutyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl. 9. The divalent platinum complex according to claim 1, characterized in that it has a structure selected from one of the following complexes 1-75: 10. Use of a divalent platinum complex according to any one of claims 1 to 9 as an electroluminescent material or a photoluminescent material. The application according to claim 10, wherein the divalent platinum complex is a blue light emitting material or a phosphorescent light emitting material. 12 . An organic optoelectronic device, comprising a light-emitting layer, wherein the light-emitting layer contains the divalent platinum complex according to any one of claims 1 to 9 . 13 . 13 . The organic optoelectronic device according to claim 12 , wherein the divalent platinum complex is a light-emitting material, a host material or a guest material in a light-emitting layer of the organic optoelectronic device. 14 .