CN111662336A - Tetradentate ring metal platinum complex phosphorescent material and organic light-emitting element - Google Patents

Tetradentate ring metal platinum complex phosphorescent material and organic light-emitting element Download PDF

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CN111662336A
CN111662336A CN202010402681.XA CN202010402681A CN111662336A CN 111662336 A CN111662336 A CN 111662336A CN 202010402681 A CN202010402681 A CN 202010402681A CN 111662336 A CN111662336 A CN 111662336A
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carbon atoms
phosphorescent material
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CN111662336B (en
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李贵杰
佘远斌
湛丰
赵理
张其胜
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Zhejiang Hongwu Technology Co ltd
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Abstract

The invention provides a quadridentate ring metal platinum complex phosphorescent material and an organic light-emitting element. The chemical formula of the phosphorescent material is shown as a general formula (1):
Figure DDA0002490096250000011
wherein R is11To R36Each independently represents a hydrogen atom or a substituent, R11To R36Two or more of which may be joined to form a fused ring, which may also be fused with other rings. The invention can effectively regulate and control the rail energy levels of the highest occupied molecular orbit and the lowest unoccupied molecular orbit of the phosphorescent material through the ligand structure and the electrical regulation of the substituent thereofThe phosphorescence material adopts a tetradentate ligand, the molecular rigidity is strong, the energy consumed by molecular vibration can be effectively reduced, the non-radiative decay is reduced, and the phosphorescence quantum efficiency is high; the parent nucleus in the chemical structure of the phosphorescent material adopts a tetradentate ligand which is linked based on nitrogen atoms and only contains a benzene ring and a pyridine ring, so that the light stability of the luminescent material can be improved.

Description

Tetradentate ring metal platinum complex phosphorescent material and organic light-emitting element
Technical Field
The invention relates to a phosphorescent material and a luminescent element, in particular to a tetradentate ring metal platinum complex phosphorescent material and an organic luminescent element.
Background
The OLED, i.e., an Organic Light-Emitting Diode (Organic Light-Emitting Diode) or an Organic Light-Emitting Device (Organic Light-Emitting Device), is an autonomous Light-Emitting Device without a backlight source; the driving voltage is low, the response speed is high, the resolution and the contrast are high, and the visual angle is wide; cheap glass, flexible plastic and metal can be used as the substrate; in addition, the method also has the advantages of low cost, simple production process, large-area production and the like. Therefore, the OLED has become a new generation of full-color display and illumination technology, and has a wide and huge application prospect in high-end electronic products and aerospace; and there is also a large potential market in the area of planar solid state lighting.
The light emitting material is the core material of the OLED device. In early OLED devices, the light-emitting material was mainly organic small molecule fluorescent material. Spin statistical quantum, however, indicates that, in the case of electroluminescence, the theoretical internal quantum efficiency is only 25% because the fluorescent material can only utilize excitons in the singlet excited state (exiton). Professor Forrest at princeton university in the united states and professor Thompson at university of southern california discovered the phenomenon of phosphorescent electroluminescence of platinum organometallic complex molecules at room temperature. Due to the strong spin-orbit coupling of heavy metal atoms, the complex can effectively promote the system leap (ISC) of excitons from singlet states to triplet states, so that the OLED device can fully utilize electric excitation to generate all singlet states and triplet states excitons, the theoretical internal quantum efficiency of the luminescent material can reach 100% (Nature,1998,395,151), and the development of the OLED luminescent material enters a new period. The development of stable and efficient novel phosphorescent light-emitting materials still has great significance for the development of the OLED industry.
Disclosure of Invention
The invention aims to provide a tetradentate ring metal platinum complex phosphorescent material and an organic light-emitting element in order to develop more varieties of phosphorescent materials with higher performance.
The invention provides a quadridentate ring metal platinum complex phosphorescent material which comprises a compound represented by the following general formula (1),
Figure BDA0002490096230000021
wherein R is11、R12、R21、R22、R23、R24、R25、R26、R31、R32、R33、R34、R35And R36Each independently represents a hydrogen atom or a substituent, R11、R12、R21、R22、R23、R24、R25、R26、R31、R32、R33、R34、R35And R36Two or more of which may be joined to form a fused ring, which may also be fused with other rings. The parent nucleus in the chemical structure of the phosphorescent material adopts a tetradentate ligand which is linked based on nitrogen atoms and only contains a benzene ring and a pyridine ring, so that the light stability of the luminescent material can be improved.
Preferably, R of said formula (1)11、R12At least one ofIs a benzene ring.
Preferably, R of said formula (1)11And R12Are the same substituents.
Preferably, R of said formula (1)21、R22、R23At least two of which are hydrogen atoms, R24、R25、R26At least two of which are hydrogen atoms, R31、R32、R33At least two of which are hydrogen atoms, R34、R35、R36At least two of which are hydrogen atoms.
Preferably, the general formula (1) is specifically a compound represented by the following general formula (2),
Figure BDA0002490096230000022
wherein A is1、A2At least one of them represents a single bond or a divalent linking group; a. the3、A4At least one of them represents a single bond or a divalent linking group; r22、R23、R24、R25、R32、R33、R34、R35、R41、R42、R43、R44、R45And R46Each independently represents a hydrogen atom or a substituent.
Preferably, the general formula (2) is specifically a compound represented by the following general formula (3),
Figure BDA0002490096230000031
wherein A is3、A4At least one of them represents a single bond or a divalent linking group; r35Represents a hydrogen atom or a substituent.
Preferably, the substituent is a substituent selected from the group consisting of: an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a sulfonyl group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a nitro group and a 5-to 7-membered heterocyclic group. Preferably, the structural formula of the quadridentate ring metal platinum complex phosphorescent material is as follows:
Figure BDA0002490096230000032
the divalent linking group is independently selected from the group consisting of: -CR1aR2a-、-CR1aR2a-CR3aR4a-、-CR1aR2a-CR3aR4a-CR5aR6a-、-CR1aR2a-NR3a-、-CR1a＝CR2a-CR3aR4a-、-O-SiR1aR2a-、-CRlaR2a-S-、-CR1aR2a-O-and-C-SiR1aR2a-, wherein each R1aTo R6aMay be the same or different and is independently selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; wherein any adjacent R1aTo R6aOptionally joined to form a saturated five-membered ring or a saturated six-membered ring.
Another object of the present invention is to provide an organic light-emitting device having a light-emitting layer of the above-described tetradentate ring platinum complex phosphorescent material on a substrate.
Compared with the prior art, the invention has the beneficial effects that:
(1) the electronic regulation of the ligand structure and the substituent thereof can effectively regulate and control the orbital energy levels of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) of the phosphorescent material.
(2) The phosphorescence luminescent material adopts the tetradentate ligand, has strong molecular rigidity, can effectively reduce the energy consumed by molecular vibration, reduces non-radiative decay, and has high phosphorescence quantum efficiency.
(3) The ligands of the phosphorescent material are all linked by nitrogen atoms and only contain benzene ring and pyridine ring structural units with stable structures, so that the stability of the material is improved.
Drawings
FIG. 1 shows the X-ray single crystal diffraction structure of Pt (bp-3);
FIG. 2 is a comparison of HOMO and LUMO orbital distributions of Pt (bp-1), Pt (bp-2) and Pt (bp-3) calculated by Density Functional Theory (DFT);
FIG. 3 is a comparison of HOMO and 0LUMO orbital distributions for Pt (bp-3), Pt (bp-4) and Pt (bp-5) calculated by Density Functional Theory (DFT);
FIG. 4 is a comparison of electrostatic potential graphs of Pt (bp-4) and Pt (bp-5) calculated by Density Functional Theory (DFT);
FIG. 5 is a comparison of absorption spectra of Pt (bp-1), Pt (bp-2), Pt (bp-3), Pt (bp-4) and Pt (bp-5);
FIG. 6 is a comparison of absorption spectra of Pt (bp-1), Pt (bp-5) and their ligands;
FIG. 7 is a comparison of the emission spectra of the platinum (II) metal phosphorescent material Pt (bp-1) in example 1 under various environments; wherein 2-MeTHF is 2-methyltetrahydrofuran; DCM is dichloromethane; PMMA is polymethyl methacrylate; RT represents room temperature;
FIG. 8 is a comparison of the emission spectra of the platinum (II) metal phosphorescent material Pt (bp-2) in example 2 under various environments; wherein 2-MeTHF is 2-methyltetrahydrofuran; DCM is dichloromethane; PMMA is polymethyl methacrylate; RT represents room temperature;
FIG. 9 is a comparison of the emission spectra of the platinum (II) metal phosphorescent material Pt (bp-3) in example 3 under various environments; wherein 2-MeTHF is 2-methyltetrahydrofuran; DCM is dichloromethane; PMMA is polymethyl methacrylate; RT represents room temperature;
FIG. 10 is a comparison of the emission spectra of the platinum (II) metal phosphorescent material Pt (bp-4) in example 4 under various environments; wherein 2-MeTHF is 2-methyltetrahydrofuran; DCM is dichloromethane; PMMA is polymethyl methacrylate; RT represents room temperature;
FIG. 11 is a comparison of the emission spectra of the platinum (II) metal phosphorescent material Pt (bp-5) in example 5 under various environments; wherein 2-MeTHF is 2-methyltetrahydrofuran; DCM is dichloromethane; PMMA is polymethyl methacrylate; RT represents room temperature;
FIG. 12 is a comparison of transient decay spectra of the phosphorescent light-emitting material Pt (bp-3) under various environments; wherein 2-MeTHF is 2-methyltetrahydrofuran; DCM is dichloromethane; PMMA is polymethyl methacrylate; RT represents room temperature;
FIG. 13 is a comparison of transient decay spectra of phosphorescent light emitting materials Pt (bp-1), Pt (bp-2), Pt (bp-4) and Pt (bp-5) under various environments; wherein 2-MeTHF is 2-methyltetrahydrofuran; DCM is dichloromethane; PMMA is polymethyl methacrylate; RT represents room temperature;
FIG. 14 is a graph showing a comparison of the photostability of a phosphorescent light-emitting material 5% Pt (bp-2) polystyrene thin film and 5% PtON1 polystyrene thin film under excitation of 375nm ultraviolet light (light intensity: 500W/m 2);
fig. 15 is a schematic structural view of an organic light-emitting element.
Detailed Description
The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment or specific example of the present invention, but the present invention is not limited to such an embodiment or specific example.
The compound contained in the tetradentate ring metal platinum complex phosphorescent material has a structure represented by the following general formula (1).
Figure BDA0002490096230000051
Wherein R is11、R12、R21、R22、R23、R24、R25、R26、R31、R32、R33、R34、R35And R36Each independently represents a hydrogen atom or a substituent selected from the group consisting of: alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, amino group having 0 to 20 carbon atoms, amino group having 1 to 20 carbon atomsAn alkoxy group, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a sulfonyl group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a nitro group and a 5-to 7-membered heterocyclic group.
R11、R12、R21、R22、R23、R24、R25、R26、R31、R32、R33、R34、R35And R36Two or more of which may be joined to form a fused ring, which may also be fused with other rings.
In the specific practice of the present invention, the alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms; e.g., methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl or cyclohexyl), alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms; e.g., vinyl, allyl, 2-butenyl or 3-pentenyl), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms; e.g., propargyl or 3-pentynyl), aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms; for example, phenyl, p-methylphenyl, naphthyl or anthracenyl), amino (preferably containing from 0 to 30 carbon atoms, more preferably from 0 to 20 carbon atoms, particularly preferably from 0 to 10 carbon atoms; for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino or di-tolylamino), alkoxy (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms; for example, methoxy, ethoxy, butoxy or 2-ethylhexyloxy), aryloxy (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms; for example, phenoxy, 1-naphthoxy or 2-naphthoxy), heterocycloxy (oxy group) (preferably containing 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms; for example, pyridyloxy, pyrazinyloxy, pyrimidyloxy or quinolyloxy), acyl (preferably containing 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms; for example, acetyl, benzoyl, formyl or pivaloyl), alkoxycarbonyl (preferably containing 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms; for example, a methoxycarbonyl group or an ethoxycarbonyl group), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms; for example, a phenoxycarbonyl group), an acyloxy group (preferably containing 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms; for example, acetyloxy or benzoyloxy), acylamino (preferably containing 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms; for example, acetylamino or benzoylamino), alkoxycarbonylamino (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms; for example, methoxycarbonylamino), aryloxycarbonylamino (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms; for example, phenoxycarbonylamino), sulfonylamino (preferably containing 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms; for example, a methanesulfonylamino group or a benzenesulfonylamino group), a sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms; for example, a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group or a phenylsulfamoyl group), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms; for example, a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group or a phenylcarbamoyl group), an alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms; for example, methylthio or ethylthio), arylthio (preferably containing 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms; e.g., phenylthio), heterocyclic thio (preferably containing from 1 to 30 carbon atoms, more preferably from 1 to 20 carbon atoms, and especially preferably from 1 to 12 carbon atoms; for example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio or 2-benzothiazolylthio), sulfonyl (preferably containing 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms; for example, methanesulfonyl or toluenesulfonyl), sulfinyl (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms; for example, methanesulfinyl or benzenesulfinyl), ureido (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms; for example, ureido, methylureido or phenylureido), phosphatamido (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and especially preferably 1 to 12 carbon atoms; for example, a diethylphosphate amido group or a phenylphosphate amido group), a hydroxyl group, a mercapto group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a sulfo group, a carboxyl group, a nitro group, an oximatoxy group, a sulfinic acid group, a hydrazine group, an imino group, a heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms; containing, for example, a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom; specific examples thereof are an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a piperidyl group, a morpholinyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a carbazolyl group or an aza group (azepinyl)), a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms; for example, trimethylsilyl or triphenylsilyl), silyloxy (preferably containing 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms; e.g., trimethylsilyloxy or triphenylsilyloxy), and the like. These substituents may also be substituted.
In one embodiment of the present invention, the general formula (1) is specifically a compound represented by the following general formula (2),
Figure BDA0002490096230000071
wherein A is1、A2At least one of them represents a single bond or a divalent linking group, A3、A4ToAt least one represents a single bond or a divalent linking group; the divalent linking group is independently selected from the group consisting of: -CR1aR2a-、-CR1aR2a-CR3aR4a-、-CR1aR2a-CR3aR4a-CR5aR6a-、-CR1aR2a-NR3a-、-CR1a＝CR2a-CR3aR4a-、-O-SiR1aR2a-、-CRlaR2a-S-、-CR1aR2a-O-and-C-SiR1aR2a-, wherein each R1aTo R6aAre the same or different and are independently selected from hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, or combinations thereof; any adjacent R1aTo R6aOptionally linked to form a saturated five-membered ring or a saturated six-membered ring;
R22、R23、R24、R25、R32、R33、R34、R35、R41、R42、R43、R44、R45and R46Each independently represents a hydrogen atom or a substituent selected from the group consisting of:
an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a sulfonyl group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a nitro group and a 5-to 7-membered heterocyclic group.
In one specific implementation of the present invention, the preferable structural formula of the quadridentate ring metal platinum complex phosphorescent material is as follows:
Figure BDA0002490096230000081
specific examples of the phosphorescent light-emitting material of the present invention represented by the following general formula (1) are illustrated below, however, the present invention is not construed to be limited.
Unless otherwise indicated, all commercial reagents involved in the following experiments were purchased and used directly without further purification. The hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance are both in deuterated chloroform (CDCl)3) Or deuterated dimethyl sulfoxide (DMSO-d)6) The hydrogen spectrum and the carbon spectrum are measured in the solution by a nuclear magnetic resonance spectrometer with 400 or 500 MHz and 100 or 126 MHz respectively, and the chemical shifts are based on Tetramethylsilane (TMS) or residual solvent. If CDCl is used3As solvent, the hydrogen spectrum and carbon spectrum are respectively expressed in TMS (═ 0.00ppm) and CDCl3(═ 77.00ppm) as an internal standard. If DMSO-d is used6As solvents, the hydrogen spectrum and the carbon spectrum are respectively expressed in TMS (═ 0.00ppm) and DMSO-d6(═ 39.52ppm) as an internal standard. The following abbreviations (or combinations) are used to interpret the hydrogen peaks: s is singlet, d is doublet, t is triplet, q is quartet, p is quintet, m is multiplet, br is broad. High resolution mass spectra were measured on an ESI-QTOF mass spectrometer from Applied Biosystems, the sample ionization mode being electrospray ionization.
Example 1: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt (bp-1) is as follows:
Figure BDA0002490096230000091
synthesis of intermediate 1-Br to a dry three-necked flask with magnetic stirrer was added 3-bromo-9, 9-dimethyl-9, 10-dihydroacridine (2.00g, 6.94mmol, 1.00 equiv.), cuprous iodide (67mg, 0.35mmol, 5 mol%) and lithium tert-butoxide (833mg, 10.41mmol, 1.50 equiv.). Then the nitrogen was purged three times and 1-methylimidazole (57mg, 0.69mmol, 10 mol%), 2-bromopyridine (1.31g, 8.33mmol, 1.20 eq.) and toluene (30mL) were added under nitrogen blanket. And then putting the three-mouth bottle into an oil bath kettle with magnetic stirring, heating to 120 ℃ for reaction for 48 hours, and monitoring by thin-layer chromatography until the reaction of the raw materials is finished. Cooling the reaction to room temperature, diluting with ethyl acetate, washing the organic phase with water, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/dichloromethane ═ 20:1 to 10:1, 2.40g of a brown solid were obtained in 95% yield.1H NMR(500MHz，CDCl3)1.65(s，6H)，6.73(dd，J＝8.0，1.5Hz，1H)，6.79(d，J＝2.0Hz，1H)，7.00(td，J＝7.5，1.5Hz，1H)，7.03-7.07(m，1H)，7.08(dd，J＝8.0，2.0Hz，1H)，7.24-7.26(m，1H)，7.27-7.29(m，1H)，7.42-7.45(m，2H)，7.78-7.81(m，1H)，8.65-8.66(m，1H)。
Synthesis of intermediate (1-B) to a 100mL dry three-necked flask with magnetic stir bar was added 1-Br (1.40g, 3.83mmol, 1.00 eq), then the nitrogen was purged three times and tetrahydrofuran (40mL) was added under nitrogen blanket. The reaction apparatus was placed in an ethanol bath, cooled to-100 ℃ with liquid nitrogen, and then n-butyllithium (2.52mL, 4.02mmol, 1.05 equiv., 1.60mol/L n-hexane solution) was slowly added dropwise, after 1 hour of reaction, isopropyl pinacol borate (855mg, 4.60mmol, 1.20 equiv.) was added dropwise, and stirred at room temperature for 12 hours. The reaction was quenched with saturated ammonium chloride solution, extracted three times with ethyl acetate, the organic phase after separation was dried over anhydrous sodium sulfate, and the filtrate was distilled under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 50:1-20:1 gave 802mg of a white solid in 51% yield.1H NMR(500MHz，CDCl3)1.28(s，12H)，1.62(s，6H)，7.01-7.05(m，2H)，7.10(td，J＝8.0，1.5Hz，1H)，7.17(ddd，J＝7.0，4.5，0.5Hz，1H)，7.28(d，J＝8.5Hz，1H)，7.39(s，1H)，7.43(dd，J＝8.0，1.5Hz，1H)，7.46(d，J＝8.0Hz，1H)，7.50(dd，J＝7.5，1.0Hz，1H)，7.76(td，J＝8.0，2.0Hz，1H)，8.62(dd，J＝5.0，1.5Hz，1H)。
Synthesis of ligand L (bp-1) to a dry three-necked flask with magnetic stirrer was added 1-B (800mg, 1.94mmol, 1.05 equiv.), 1-Br (676mg, 1.85mmol, 1.00 equiv.), palladium tetrakistriphenylphosphine (64mg, 0.056mmol, 3 mol%) and potassium carbonate (639mg, 4.63mmol, 2.5 equiv). The nitrogen was then purged three times and 1, 4-dioxane (12mL) and water (3mL) were added under nitrogen. Then the three-mouth bottle is put into an oil bath pot with magnetic stirring, the temperature is raised to 85 ℃ for reaction for 48 hours,and monitoring by thin-layer chromatography until the reaction of the raw materials is finished. Cooling the reaction to room temperature, distilling under reduced pressure to remove the solvent, adding ethyl acetate for dilution, washing the organic phase with water, drying the organic phase with anhydrous sodium sulfate after liquid separation, and distilling the filtrate under reduced pressure to remove the solvent after filtration. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 20:1-10:1 gave 613mg of a white solid in 58% yield.1H NMR(500MHz，DMSO-d6)1.60(s，12H)，6.25(d，J＝2.0Hz，2H)，6.32(dd，J＝8.0，1.5Hz，2H)，6.96(td，J＝7.5，1.5Hz，2H)，7.01(td，J＝8.0，2.0Hz，2H)，7.07(dd，J＝8.0，2.0Hz，2H)，7.38(dt，J＝8.0，1.0Hz，2H)，7.49(dd，J＝7.5，1.5Hz，2H)，7.51(d，J＝8.5Hz，2H)，7.60(ddd，J＝7.5，5.0，1.0Hz，2H)，8.08(td，J＝75，2.0Hz，2H)，8.71(ddd，J＝4.5，2.0，0.5Hz，2H)。13C NMR(125MHz，DMSO-d6)30.65，35.68，113.10，115.25，119.58，121.53，123.06，123.17，125.19，125.87,126.30，130.72，131.40，138.16，139.56，140.07，140.36，150.69，153.99。HRMS(ESI)：C40H35N4[M+H]+Calculated 571.2856, found 571.2875.
Synthesis of Pt (bp-1) to a dry three-necked flask with magnetic stirrer, L (bp-1) (300mg, 0.53mmol, 1.00 equiv.) and platinum dichloride (147mg, 0.55mmol, 1.05 equiv.) were added, then nitrogen was purged three times and benzonitrile (40mL) was added under nitrogen. The three-necked flask is put into an oil bath kettle with magnetic stirring, the temperature is increased to 180 ℃ for reaction for 60 hours, the reaction is cooled to room temperature, tetrahydrofuran (12mL) and potassium tert-butoxide (1.18g, 10.51mmol and 20.00 equivalents) are added under the protection of nitrogen, and the temperature is increased to 76 ℃ for reaction for 5 hours. The reaction was cooled to room temperature and then concentrated in vacuo. The crude product was diluted with dichloromethane, washed with water and extracted twice with dichloromethane. The organic phases were combined and dried over anhydrous sodium sulfate, filtered and the filtrate was distilled under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/dichloromethane ═ 5:1 to 1:1, and 351mg of a yellow solid was obtained in a yield of 87%.1H NMR(500MHz，DMSO-d6)1.30(s，6H)，1.83(s，6H)，6.91(d，J＝8.0Hz，2H)，7.05(d，J＝8.0Hz，2H)，7.17(td，J＝7.5，1.5Hz，2H)，7.21(td，J＝8.0，1.5Hz，2H)，7.25-7.28(m，4H)，7.44(d，J＝8.0Hz，2H)，7.51(dd，J＝7.5，1.5Hz，2H)，7.95-7.98(m，2H)，8.82(dd，J＝5.5，2.0Hz，2H)。HRMS(ESI)：C40H33N4Pt[M+H]+Calculated 764.2347, found 764.2318. Elemental analysis: c40H32N4Calculated Pt: c, 62.90; h, 4.22; n, 7.34; measured value: c, 63.03; h, 4.35; and N, 7.11.
Example 2: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt (bp-2) is as follows:
Figure BDA0002490096230000111
synthesis of intermediate (2-Br) 5, 5-dimethyl-5, 10-dihydrobenzo [ b ] was added to a dry three-necked flask with a magnetic stirrer][1,8]Naphthyridine (1.66g, 7.90mmol, 1.0 equiv.), cuprous iodide (301mg, 1.58mmol, 10 mol%), L-proline (273mg, 2.37mmol, 30 mol%) and potassium carbonate (2.18g, 15.80mmol, 2.0 equiv.), nitrogen was pumped three times, 1-bromo-3-iodobenzene (3.35g, 11.84mmol, 1.5 equiv.) and dimethyl sulfoxide (35mL) were added under nitrogen protection, the three-necked flask was placed in an oil bath with magnetic stirring, the temperature was raised to 110 ℃ for reaction for 60 hours, and thin layer chromatography was used to monitor that the reaction of the raw materials was complete. The reaction was cooled to room temperature, diluted with ethyl acetate, the organic phase was washed with water, the organic phase was dried over anhydrous sodium sulfate after separation, and the filtrate was filtered and distilled under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 20:1-10:1 gave 2.19g of a white solid in 76% yield.1H NMR(500MHz，CDCl3)1.67(s，6H)，6.28-6.31(m，1H)，6.86-6.89(m，1H)，6.98-7.05(m，2H)，7.32-7.34(m，1H)，7.45(dd，J＝7.5，2.0Hz，1H)，7.48(t，J＝8.0Hz，1H)，7.53(t，J＝2.0Hz，1H)，7.60-7.63(m，1H)，7.68(dd，J＝7.5，2.0Hz，1H)，8.02(dd，J＝4.5，1.5Hz，1H)。
Synthesis of ligand L (bp-2): stirring by magnetic forceA dry three-neck flask was charged with 1-B (1.00g, 2.43mmol, 1.00 equiv.), 2-Br (888mg, 2.43mmol, 1.00 equiv.), palladium tetratriphenylphosphine (84mg, 0.073mmol, 3 mol%) and potassium carbonate (838mg, 6.06mmol, 2.5 equiv.), purged with nitrogen three times, charged with 1, 4-dioxane (14mL) and water (3mL) under nitrogen, placed in a magnetically stirred oil bath, allowed to warm to 100 ℃ for 36 hours and monitored by thin layer chromatography until the starting material was reacted. Cooling the reaction to room temperature, distilling under reduced pressure to remove the solvent, adding ethyl acetate for dilution, washing the organic phase with water, drying the organic phase with anhydrous sodium sulfate after liquid separation, and distilling the filtrate under reduced pressure to remove the solvent after filtration. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 20:1-5:1 gave 1.00g of white solid in 72% yield.1H NMR(500MHz，DMSO-d6)1.62(d，J＝3.5Hz，12H)，6.21(dd，J＝8.0，2.0Hz，1H)，6.52(dd，J＝8.0，1.5Hz，1H)，6.79(d，J＝2.0Hz，1H)，6.92-7.02(m，4H)，7.06(td，J＝7.5，1.5Hz，1H)，7.26-7.27(m，1H)，7.32(dd，J＝8.0，1.5Hz，1H)，7.35(t，J＝2.0Hz，1H)，7.42(ddd，J＝7.5，5，1.0Hz，1H)，7.46(d，J＝8.0Hz，1H)，7.51(td，J＝7.5，1.5Hz，3H)，7.56-7.62(m，2H)，7.84(dd，J＝8.0，2.0Hz，1H)，7.89(dd，J＝4.5，1.5Hz，1H)，8.00(td，J＝7.5，2.0Hz，1H)，8.66-8.68(m，1H)。13C NMR(125MHz，DMSO-d6)30.15，30.74，35.87，35.90，114.54，116.36，116.91，120.24，121.39，121.95，122.02，122.34，124.58，125.01，125.29，125.40，125.74，126.31，126.74，128.77，129.62，129.78，130.54，132.18，132.50，133.53，137.54，139.72，140.09，140.17，140.31，140.87，141.90，144.99，145.07，150.31，150.85，154.39。HRMS(ESI)：C40H35N4[M+H]+Calculated 571.2856, found 571.2876.
Synthesis of Pt (bp-2) to a dry three-necked flask with magnetic stirrer were added L (bp-2) (200mg, 0.35mmol, 1.0 equiv.), potassium tetrachloroplatinate (161mg, 0.39mmol,1.1 equiv.) and tetrabutylammonium bromide (11mg, 0.035mmol, 10 mol%), nitrogen was purged three times, and under nitrogen protectionAcetic acid (25mL) was added. The reaction solution was bubbled with nitrogen for 30 minutes and then stirred at room temperature for 12 hours. The three-mouth bottle is put into an oil bath kettle with magnetic stirring, and the temperature is raised to 130 ℃ for reaction for 72 hours. The reaction was cooled to room temperature, the solvent was distilled off under reduced pressure, dichloromethane was added for dilution, the organic phase was washed with water, the organic phase was dried over anhydrous sodium sulfate after separation, and the filtrate was distilled off under reduced pressure to remove the solvent after filtration. The crude product and stannous chloride (332mg, 1.75mmol, 5.00 equiv.) were added to a dry three-necked flask with magnetic stirrer, nitrogen was purged three times, and 1, 2-dichloroethane (35mL) was added under nitrogen protection for reaction at room temperature for 72 hours. The reaction solution was washed with water, the organic phase after separation was dried over anhydrous sodium sulfate, and the filtrate was filtered to remove the solvent by distillation under reduced pressure. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/dichloromethane/ethyl acetate 8:2:1 gave 45mg of a yellow solid in 17% yield.1H NMR(500MHz，DMSO-d6)1.32(d，J＝3.0Hz，6H)，1.86(s，3H)，1.95(s，3H)，6.60(d，J＝8.0Hz，1H)，6.83(t，J＝8.0Hz1H)，6.97(d，J＝7.5Hz，1H)，7.09-7.27(m，9H)，7.33(dd，J＝7.5，5.5Hz，1H)，7.42(d，J＝8.5Hz，1H)，7.53(td，J＝7.5，2.0Hz，2H)，7.92-7.95(m，1H)，8.19(dd，J＝7.5，1.5Hz，1H)，8.53(dd，J＝5.5，1.5Hz，1H)，8.70(dd，J＝5.5，1.5Hz，1H)。HRMS(ESI)：C40H32N4Pt[M+H]+Calculated 764.2347, found 764.2341. Elemental analysis: c40H32N4Pt·0.5CH2Cl2Calcd for C, 60.33, H, 4.13, N, 6.95; found C, 61.14, H, 4.93, N, 6.20.
Example 3: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt (bp-3) is as follows:
Figure BDA0002490096230000131
synthesis of intermediate (3-Br): adding 9H-pyrido [2,3-b ] into a dry three-necked flask with a magnetic stirrer]Indole (4.00g, 23.78mmol, 1.00 equiv.), cuprous iodide (906mg, 4.76mmol, 20 mol%), L-proline (548mg, 4 mol%), N-proline76mmol, 20 mol%) and potassium carbonate (6.57g, 47.56mmol, 2.0 eq), nitrogen was purged three times, 1-bromo-3-iodobenzene (10.09g, 35.67mmol, 1.5 eq) and dimethyl sulfoxide (50mL) were added under nitrogen protection, the three-necked flask was placed in an oil bath with magnetic stirring, the temperature was raised to 120 ℃ for reaction for 72 hours, and thin layer chromatography was monitored until the reaction of the starting materials was complete. The reaction was cooled to room temperature, diluted with ethyl acetate, the organic phase was washed with water, the organic phase was dried over anhydrous sodium sulfate after separation, and the filtrate was filtered and distilled under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 25:1-10:1 to give 3.84g of a white solid in 50% yield1The product contained 19% impurities by H NMR analysis.1HNMR(500MHz，DMSO-d6)7.24-7.27(m，1H)，7.33-7.37(m，1H)，7.47-7.51(m，3H)，7.59-7.61(m，1H)，7.62-7.65(m，1H)，7.84(d，J＝2.0Hz，1H)，8.12(dd，J＝8.0，1.0Hz，1H)，8.37-8.40(m，1H)，8.47-8.49(m，1H)。
Synthesis of intermediate (3-B) to a dry three-necked flask with magnetic stirrer was added 3-Br (1.62g, 5.00mmol, 1.00 eq), nitrogen was purged three times, and tetrahydrofuran (40mL) was added under nitrogen blanket. The reaction apparatus was placed in an ethanol bath, cooled to-76 ℃ with liquid nitrogen, and then n-butyllithium (3.44mL, 5.50mmol, 1.10 equiv., 1.60mol/L n-hexane solution) was slowly added dropwise, after 1 hour of reaction, isopropyl pinacol borate (855mg, 4.60mmol, 1.20 equiv.) was added dropwise, and stirred at room temperature for 12 hours. The reaction was quenched with saturated ammonium chloride solution, extracted three times with ethyl acetate, the organic phase after separation was dried over anhydrous sodium sulfate, and the filtrate was distilled under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 40:1-10:1 gave 1.30g of a white solid in 70% yield.1H NMR(500MHz，CDCl3)1.34(s，12H)，7.22(dd，J＝7.5，5.0Hz，1H)，7.30-7.34(m，1H)，7.42(dt，J＝8.0，1.0Hz，1H)，7.45-7.48(m，1H)，7.63(t，J＝8.0Hz，1H)，7.72(ddd，J＝7.5，2.0，1.0Hz，1H)，7.92(dt，J＝7.5，1.5Hz，1H)，8.03(dd，J＝2.5，1.0Hz，1H)，8.12(dt，J＝7.5，1.0Hz，1H)，8.38(dd，J＝7.5，1.5Hz，1H)，8.48(dd，J＝4.5，1.5Hz，1H)。13C NMR(125MHz，CDCl3)24.74，24.82，83.91，110.35，115.83，116.19，120.53，120.64，120.76，126.81，128.11，129.04，130.47，133.68，134.10，135.78，140.25，146.37，152.03。
Synthesis of ligand L (bp-3): a dry three-necked flask with a magnetic stirrer was charged with 3-B (1.55g, 4.24mmol, 1.00 equiv.), 1-Br (1.57g, 4.24mmol, 1.00 equiv.), palladium tetratriphenylphosphine (147mg, 0.13mmol, 3 mol%) and potassium carbonate (1.46g, 10.60mmol, 2.5 equiv.), nitrogen was purged three times, 1, 4-dioxane (15mL) and water (5mL) were added under nitrogen, the three-necked flask was placed in an oil bath with magnetic stirring, the temperature was raised to 100 ℃ for reaction for 24 hours, and thin layer chromatography was used to monitor that the starting material was reacted. Cooling the reaction to room temperature, distilling under reduced pressure to remove the solvent, adding ethyl acetate for dilution, washing the organic phase with water, drying the organic phase with anhydrous sodium sulfate after liquid separation, and distilling the filtrate under reduced pressure to remove the solvent after filtration. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 15:1-5:1 gave 1.34g of a tan solid in 60% yield.1H NMR(500MHz，CDCl3)1.69(s，6H)，6.75(dd，J＝8.0，1.5Hz，1H)，7.02(td，J＝7.5，1.5Hz，1H)，7.05-7.08(m，2H)，7.22-7.25(m，2H)，7.27(td，J＝8.0，2.0Hz，1H)，7.31-7.35(m，2H)，7.43-7.49(m，3H)，7.51-7.54(m，2H)，7.57-7.61(m，2H)，7.72(t，J＝2.0Hz，1H)，7.81(td，J＝7.5，2.0Hz，1H)，8.13(dt，J＝7.5，1.0Hz，1H)，8.39(dd，J＝7.5，1.5Hz，1H)，8.46(dd，J＝5.0，2.0Hz，1H)，8.67(ddd，J＝5.0，2.0，0.5Hz，1H)。13C NMR(125MHz，CDCl3)29.94，36.31，110.28，115.93，116.09，116.17，117.23，120.60，120.68，120.77，121.00，121.15，121.20，122.14，124.62，125.17，125.65，125.80，126.12，126.15，126.81，128.08，129.69，133.27，133.60，136.37，138.43，139.06，139.82，140.16，140.61，142.66，146.29，150.11，151.71，155.24。HRMS(ESI)：C37H29N4[M+H]+Calculated 529.2387, found 529.2404.
Synthesis of Pt (bp-3): to a dry three-necked flask with a magnetic stir bar, L (bp-3) (300mg, 0.57mmol, 1.0 equiv.), potassium tetrachloroplatinate (259mg, 0.62mmol,1.1 equiv.), and tetrabutylammonium bromide (18mg, 0.057mmol, 10 mol%) were added, nitrogen was purged three times, and acetic acid (30mL) was added under nitrogen blanket. The reaction solution was bubbled with nitrogen for 30 minutes and then stirred at room temperature for 12 hours. The three-mouth bottle is put into an oil bath kettle with magnetic stirring, and the temperature is raised to 130 ℃ for reaction for 72 hours. The reaction was cooled to room temperature, the solvent was distilled off under reduced pressure, dichloromethane was added for dilution, the organic phase was washed with water, the organic phase was dried over anhydrous sodium sulfate after separation, and the filtrate was distilled off under reduced pressure to remove the solvent after filtration. The crude product and stannous chloride (538mg, 2.84mmol, 5.00 equiv.) were added to a dry three-necked flask with magnetic stirrer, nitrogen was purged three times, and 1, 2-dichloroethane (30mL) and acetic acid (15mL) were added under nitrogen for 84 hours at room temperature. The reaction solution was washed with water, the organic phase after separation was dried over anhydrous sodium sulfate, and the filtrate was filtered to remove the solvent by distillation under reduced pressure. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/dichloromethane/ethyl acetate 8:2:1 gave 70mg of yellow solid in 17% yield.1H NMR(500MHz，DMSO-d6)1.30(s，3H)，1.87(s，3H)，7.00(d，J＝8.0Hz，1H)，7.13(t，J＝7.5Hz，1H)，7.18-7.20(m，3H)，7.25(td，J＝7.5，1.5Hz，1H)，7.28(d，J＝7.0Hz，1H)，7.34(dd，J＝8.0，1.5Hz，1H)，7.46(d，J＝8.5Hz，1H)，7.52(t，J＝7.5Hz，1H)，7.55(dd，J＝8.0，2.0Hz，1H)，7.61(dd，J＝7.5，6.0Hz，1H)，7.68-7.71(m，1H)，7.75(d，J＝8.0Hz，1H)，7.93-7.97(m，1H)，8.37(d，J＝8.5Hz，1H)，8.46-8.50(m，2H)，8.89(dd，J＝5.5，1.5Hz，1H)，9.07(dd，J＝8.0，1.5Hz，1H)。HRMS(ESI)：C37H27N4Pt[M+H]+Calculated 722.1878, found 722.1866. Elemental analysis: c37H26N4Pt·0.4CH2Cl2Calcd for C, 59.44, H, 3.57, N, 7.41; found C, 59.19, H, 3.99, N, 7.26. The X-ray single crystal diffraction structure of Pt (bp-3) is shown in FIG. 1.
Example 4: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt (bp-4) is as follows:
Figure BDA0002490096230000151
synthesis of intermediate (4-Br): adding 9H-pyrido [2,3-b ] into a dry three-necked flask with a magnetic stirrer]Indole (5.05g, 30.00mmol, 1.00 equiv.), 1, 3-dibromo-5- (tert-butyl) benzene (13.14g, 45.00mmol, 1.5 equiv.), cuprous iodide (571mg, 3.00mmol, 10 mol%), L-proline (690mg, 6.00mmol, 20 mol%) and potassium carbonate (8.29g, 60.00mmol, 2.0 equiv.), nitrogen was pumped three times, dimethyl sulfoxide (50mL) was added under nitrogen protection, the three-necked flask was placed in an oil bath with magnetic stirring, the temperature was raised to 120 ℃ for reaction for 24 hours, and thin layer chromatography was used to monitor that the reaction of the raw materials was completed. The reaction was cooled to room temperature, diluted with ethyl acetate, the organic phase was washed with water, the organic phase was dried over anhydrous sodium sulfate after separation, and the filtrate was filtered and distilled under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 40:1-20:1 gave 4.03g of a white solid in 35% yield.1H NMR(500MHz，CDCl3)1.38(s，9H)，7.24-7.27(m，1H)，7.33-7.36(m，1H)，7.45(dt，J＝8.5，1.0Hz，1H)，7.49(td，J＝8.0，1.5Hz，1H)，7.59(t，J＝2.0Hz，1H)，7.61(t，J＝2.0Hz，1H)，7.65(t，J＝1.5Hz，1H)，8.13(dt，J＝7.5，1.0Hz，1H)，8.39(dd，J＝7.5，1.5Hz，1H)，8.48(dd，J＝5.0，1.5Hz，1H)。13C NMR(125MHz，CDCl3)31.25，35.22，110.29，116.36，116.40，120.98，121.01，121.07，122.83，123.50，127.14，127.68，128.05，128.35，137.21，139.90，146.60，151.80，154.63。
Synthesis of intermediate (4-B) to a dry three-necked flask with magnetic stirrer was added 4-Br (2.28g, 6.00mmol, 1.00 eq), nitrogen was purged three times, and tetrahydrofuran (40mL) was added under nitrogen blanket. The reaction device is placed in an ethanol bath, liquid nitrogen is used for cooling to-76 ℃, then n-butyllithium (3.94mL, 6.30mmol, 1.05 equivalent and 1.60mol/L n-hexane solution) is slowly dripped, and isopropanol is dripped after 1 hour of reactionNaphthoroborate (1.23g, 6.60mmol, 1.1 eq.) was stirred at room temperature for 12 h. The reaction was quenched with saturated ammonium chloride solution, extracted three times with ethyl acetate, the organic phase after separation was dried over anhydrous sodium sulfate, and the filtrate was distilled under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 50:1-10:1 gave 1.79g of a white solid in 70% yield.1H NMR(500MHz，CDCl3)1.34(s，12H)，1.40(s，9H)，7.21(dd，J＝7.5，5.0Hz，1H)，7.32(t，J＝7.5Hz，1H)，7.38(d，J＝8.0Hz，1H)，7.46(t，J＝8.0Hz，1H)，7.70(t，J＝2.0Hz，1H)，7.85(s，1H)，7.93(s，1H)，8.12(d，J＝7.5Hz，1H)，8.38(dd，J＝7.5，1.5Hz，1H)，8.48(dd，J＝5.0，1.5Hz，1H)。13C NMR(125MHz，CDCl3)25.00，31.51，35.03，83.95，110.49，115.85，116.25，120.54，120.78，120.92，126.91，127.87，128.20，131.21，131.27，135.67，140.63，146.63，152.18，152.30.
Synthesis of ligand L (bp-4): a dry three-necked flask with a magnetic stirrer was charged with 4-B (1.50g, 3.52mmol, 1.00 equiv.), 1-Br (1.29g, 3.52mmol, 1.00 equiv.), palladium tetratriphenylphosphine (127mg, 0.11mmol, 3 mol%) and potassium carbonate (1.22g, 8.80mmol, 2.5 equiv.), nitrogen was purged three times, 1, 4-dioxane (13mL) and water (5mL) were added under nitrogen, the three-necked flask was placed in an oil bath with magnetic stirring, the temperature was raised to 100 ℃ for reaction for 36 hours, and thin layer chromatography was used to monitor that the starting material was reacted. Cooling the reaction to room temperature, distilling under reduced pressure to remove the solvent, adding ethyl acetate for dilution, washing the organic phase with water, drying the organic phase with anhydrous sodium sulfate after liquid separation, and distilling the filtrate under reduced pressure to remove the solvent after filtration. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 20:1-10:1 gave 1.44g of a white solid in 70% yield.1H NMR(500MHz，DMSO-d6)1.35(s，9H)，1.64(s，6H)，6.49(dd，J＝8.0，1.5Hz，1H)，6.77(d，J＝1.5Hz，1H)，7.01(td，J＝7.5，1.5Hz，1H)，7.06(td，J＝8.0，2.0Hz，1H)，7.33-7.39(m，3H)，7.46(d，J＝8.0Hz，1H)，7.48-7.54(m，6H)，7.58-7.62(m，2H)，8.05(td，J＝7.5，2.0Hz，1H)，8.31(d，J＝8.0Hz，1H)，8.41(dd，J＝5.0，1.5Hz，1H)，8.65(dd，J＝7.5，1.5Hz，1H)，8.69-8.73(m，1H)。13C NMR(125MHz，DMSO-d6)26.28，30.39，30.92，34.67，35.85，110.01，114.63，115.61，116.04，116.46，120.30，120.37，120.80，121.46，121.82，122.35，122.43，122.48，122.50，122.68，125.12，125.83，126.32，127.24，128.83，131.83，132.14，136.06，138.19，139.11，139.64，140.13，140.26，141.23，146.32，150.39，151.10，152.67，154.35。HRMS(ESI)：C41H37N4[M+H]+Calculated 585.3013, found 585.3031.
Synthesis of Pt (bp-4): to a dry three-necked flask with a magnetic stir bar, L (bp-4) (300mg, 0.51mmol, 1.0 equiv.), potassium tetrachloroplatinate (234mg, 0.56mmol, 1.1 equiv.), and tetrabutylammonium bromide (17mg, 0.051mmol, 10 mol%) were added, nitrogen was purged three times, and acetic acid (30mL) was added under nitrogen blanket. The reaction solution was bubbled with nitrogen for 30 minutes and then stirred at room temperature for 12 hours. Putting the three-necked bottle into an oil bath kettle with magnetic stirring, and heating to 125 ℃ for reaction for 96 hours. The reaction was cooled to room temperature, the solvent was distilled off under reduced pressure, dichloromethane was added for dilution, the organic phase was washed with water, the organic phase was dried over anhydrous sodium sulfate after separation, and the filtrate was distilled off under reduced pressure to remove the solvent after filtration. The crude product and stannous chloride (483mg, 2.55mmol, 5.00 equiv.) were added to a dry three-necked flask with magnetic stirrer, nitrogen was purged three times, and 1, 2-dichloroethane (50mL) was added under nitrogen protection to react at room temperature for 48 hours. The reaction solution was washed with water, the organic phase after separation was dried over anhydrous sodium sulfate, and the filtrate was filtered to remove the solvent by distillation under reduced pressure. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/dichloromethane/ethyl acetate 8:2:1 gave 63mg of a yellow solid in 16% yield.1H NMR(500MHz，DMSO-d6)1.30(s，3H)，1.41(s，9H)，1.87(s，3H)，6.99(d，J＝7.5Hz，1H)，7.18-7.22(m，2H)，7.23-7.26(m，2H)，7.32-7.34(m，2H)，7.45(d，J＝8.5Hz，1H)，7.51(d，J＝8.0，1H)，7.53-7.56(m，1H)，7.61(dd，J＝7.5，5.5Hz，1H)，7.72-7.76(m，2H)，7.93-7.97(m，1H)，8.32(d，J＝8.5Hz，1H)，8.48-8.51(m，2H)，8.89(dd，J＝5.0，1.0Hz，1H)，9.07(dd，J＝7.5，1.5Hz，1H)。HRMS(ESI)：C41H35N4Pt[M+H]+Calculated 778.2504, found 778.2480. Elemental analysis: c41H34N4Pt·0.25CH2Cl2Calculated values of C, 62.00, H, 4.35, N, 7.01; found C, 62.55, H, 5.35, N, 5.59.
Example 5: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt (bp-5) is as follows:
Figure BDA0002490096230000171
synthesis of intermediate (5-Br): adding 9H-pyrido [2,3-b ] into a dry three-necked flask with a magnetic stirrer]Indole (5.05g, 30.00mmol, 1.00 equiv.), cuprous iodide (571mg, 3.00mmol, 10 mol%), L-proline (690mg, 6.00mmol, 20 mol%) and potassium carbonate (8.29g, 60.00mmol, 2.0 equiv.), nitrogen was pumped three times, 1, 3-dibromo-5- (trifluoromethyl) benzene (11.85g, 39.00mmol, 1.3 equiv.) and dimethyl sulfoxide (50mL) were added under nitrogen protection, the three-necked flask was placed in an oil bath with magnetic stirring, the temperature was raised to 120 ℃ for reaction for 24 hours, and thin layer chromatography was used to monitor that the reaction of the raw materials was complete. The reaction was cooled to room temperature, diluted with ethyl acetate, the organic phase was washed with water, the organic phase was dried over anhydrous sodium sulfate after separation, and the filtrate was filtered and distilled under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 50:1-20:1 gave 4.70g of a white solid in 40% yield.1H NMR(500MHz，CDCl3)7.30(dd，J＝7.5，5.0Hz，1H)，7.37-7.41(m，1H)，7.48-7.55(m，2H)，7.85(s，1H)，7.94(s，1H)，8.09(t，J＝2.0Hz，1H)，8.13(dt，J＝7.5，1.0Hz，1H)，8.40(dd，J＝7.5，1.5Hz，1H)，8.48(dd，J＝5.0，1.5Hz，1H)。13C NMR(125MHz，CDCl3)110.02，116.70，117.12，121.33，121.37，121.75，122.86(q，J＝3.75Hz)，123.05(q，J＝271.25Hz)，123.44，127.22(q，J＝3.75Hz)，127.50，128.58，133.40(q，J＝33.75Hz)，133.57，138.31，139.15，146.63，151.49。
Synthesis of intermediate (5-B) to a dry three-necked flask with magnetic stirrer was added 5-Br (2.74g, 7.00mmol, 1.00 eq.), the nitrogen was purged three times and tetrahydrofuran (40mL) was added under nitrogen blanket. The reaction apparatus was placed in an ethanol bath, cooled to-76 ℃ with liquid nitrogen, and then n-butyllithium (4.59mL, 7.35mmol, 1.05 equiv., 1.60mol/L n-hexane solution) was slowly added dropwise, after 1 hour of reaction, isopropanol pinacol borate (1.43g, 7.70mmol, 1.1 equiv.) was added dropwise, and the mixture was stirred at room temperature for 12 hours. The reaction was quenched with saturated ammonium chloride solution, extracted three times with ethyl acetate, the organic phase after separation was dried over anhydrous sodium sulfate, and the filtrate was distilled under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 50:1-10:1 gave 2.01g of a white solid in 65% yield.1H NMR(500MHz，CDCl3)1.36(s，12H)，7.27(dd，J＝4.5Hz，1H)，7.34-7.37(m，1H)，7.41(d，J＝8.5Hz，1H)，7.48-7.51(m，1H)，8.00(s，1H)，8.13(d，J＝7.5Hz，1H)，8.16(s，1H)，8.24(s，1H)，8.39(dd，J＝7.5，1.5Hz，1H)，8.48(dd，J＝5.0，1.5Hz，1H)。13C NMR(125MHz，CDCl3)24.96 84.63，110.15，116.52，116.54，121.08，121.15，121.22，124.01(q，J＝271.25Hz)，127.16(q，J＝3.75Hz)，127.27，128.46，130.61(q，J＝3.75Hz)，131.74(q，J＝32.50Hz)，136.60，137.10，139.93，146.63，151.97。
Synthesis of ligand L (bp-5): a dry three-necked flask with a magnetic stirrer was charged with 5-B (1.50g, 3.42mmol, 1.00 equiv.), 1-Br (1.25g, 3.42mmol, 1.00 equiv.), palladium tetratriphenylphosphine (119mg, 0.10mmol, 3 mol%) and potassium carbonate (1.18g, 8.55mmol, 2.5 equiv.), nitrogen was purged three times, 1, 4-dioxane (13mL) and water (5mL) were added under nitrogen protection, the three-necked flask was placed in an oil bath with magnetic stirring, the temperature was raised to 100 ℃ for reaction for 24 hours, and thin layer chromatography was used to monitor that the starting material was reacted. Cooling the reaction to room temperature, distilling under reduced pressure to remove solvent, diluting with ethyl acetate, washing organic phase with water, drying the organic phase with anhydrous sodium sulfate, filtering, and filteringThe solvent was distilled off under reduced pressure. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate 40:1-10:1 gave 1.09g of white solid in 53% yield.1H NMR(500MHz，DMSO-d6)1.64(s，6H)，6.55(dd，J＝8.0，1.5Hz，1H)，6.94(d，J＝2.0Hz，1H)，7.03(td，J＝7.5，1.5Hz，1H)，7.08(td，J＝8.0，1.5Hz，1H)，7.40-7.42(m，2H),7.45-7.56(m，6H)，7.65(d，J＝8.0Hz，1H)，7.85(s，1H)，8.02-8.05(m，3H)，8.33(d，J＝8.0Hz，1H)，8.44(dd，J＝5.0，2.0Hz，1H)，8.67(dd，J＝7.5，2.0Hz，1H)，8.69-8.71(m，1H)。13C NMR(125MHz，DMSO-d6)29.89，35.94，109.78，114.99，115.90，116.56，116.97，120.57，120.69，121.25，121.39，121.42，121.50，121.76，122.06，122.24，123.70(q，J＝271.25Hz)，124.88，125.84，126.29，127.35，128.44，128.92，130.85(q，J＝32.50Hz)，132.57，133.26，136.12，137.13，138.55，139.67，139.97，140.48，142.70，146.29，150.21，150.84，154.32。HRMS(ESI)：C38H28F3N4[M+H]+Calculated 597.2261, found 597.2279.
Synthesis of Pt (bp-5): to a dry three-necked flask with a magnetic stir bar, L (bp-5) (300mg, 0.50mmol, 1.0 equiv.), potassium tetrachloroplatinate (228mg, 0.55mmol, 1.1 equiv.), and tetrabutylammonium bromide (16mg, 0.050mmol, 10 mol%) were added, nitrogen was purged three times, and acetic acid (30mL) was added under nitrogen blanket. The reaction solution was bubbled with nitrogen for 30 minutes and then stirred at room temperature for 12 hours. Putting the three-necked bottle into an oil bath kettle with magnetic stirring, and heating to 125 ℃ for reaction for 96 hours. The reaction was cooled to room temperature, the solvent was distilled off under reduced pressure, dichloromethane was added for dilution, the organic phase was washed with water, the organic phase was dried over anhydrous sodium sulfate after separation, and the filtrate was distilled off under reduced pressure to remove the solvent after filtration. The crude product and stannous chloride (474mg, 2.50mmol, 5.00 equiv.) were added to a dry three-necked flask with magnetic stirrer, nitrogen was purged three times, and 1, 2-dichloroethane (60mL) was added under nitrogen protection for 48 hours at room temperature. Washing the reaction solution with water, separating, drying the organic phase with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to removeA solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/dichloromethane/ethyl acetate 8:2:1 gave 88mg of a yellow solid in 22% yield.1H NMR(500MHz，DMSO-d6)1.31(s，3H)，1.88(s，3H)，7.05(d，J＝8.0Hz，1H)，7.19-7.24(m，2H)，7.26(td，J＝7.0，1.3Hz，1H)，7.34(d，J＝8.0Hz，1H)，7.36(dd，J＝8.0，1.5Hz，1H)，7.49(d，J＝9.0Hz，1H)，7.53-7.57(m，3H)，7.65(dd，J＝7.5，5.5Hz，1H)，7.76(td，J＝8.0，1.5Hz，1H)，7.91(s，1H)，7.95-7.98(m，1H)，8.24(d，J＝8.5Hz，1H)，8.47(dd，J＝6.0，1.5Hz，1H)，8.50(d，J＝8.0Hz，1H)，8.89(dd，J＝6.0，1.5Hz，1H)，9.09(dt，J＝7.5，1.5Hz，1H)。HRMS(ESI)：C38H26F3N4Pt[M+H]+Calculated 790.1752, found 790.1737. Elemental analysis: c38H25F3N4Pt·0.5CH2Cl2Calcd for C, 55.57, H, 3.15, N, 6.73; found C, 55.79, H, 3.49, N, 6.72.
Electrochemical, photophysical tests and theoretical calculations show that:
cyclic Voltammetry (CV) and Differential Pulse Voltammetry (DPV) characterizations were performed using a CH1760E electrochemical analyzer. The oxidation potential and reduction potential were measured using 0.1mol/L tetra-N-butylammonium hexafluorophosphate as the electrolyte and anhydrous N, N-dimethylformamide as the solvent, and the solution was bubbled with nitrogen for 15min before the test. Respectively using silver, platinum and glassy carbon as pseudo reference electrode, counter electrode and working electrode, scanning speed is 300mV/s, and ferrocene ion pair (CP)2Fe/Cp2Fe+) And (5) making an internal standard. Measuring redox potential by differential pulse voltammetry, measuring redox reversibility by cyclic voltammetry, and if the magnitudes of the peak anode current and the peak cathode current are equal when the scanning speed is 100mV/s or lower, determining that the process is reversible; if the magnitudes of the peak anode current and the peak cathode current are not equal, but the return sweep is not zero, then the process is considered to be quasi-reversible; otherwise the process is not reversible.
Absorption spectrum of the ultraviolet-visible light spectrum of Agilent 8453On-instrument measurements, steady state emission experiments and lifetime measurements were performed on a Horiba Jobin YvonFluoroLog-3 spectrometer. The low-temperature (77K) emission spectrum and lifetime were measured in a 2-methyltetrahydrofuran solution cooled with liquid nitrogen. The Pt (II) complex is theoretically calculated by using a Titan software package, and the Density Functional Theory (DFT) is used for optimizing the ground state (S)0) The geometry of the molecule was calculated by DFT using the B3LYP functional, with C, H, O and N atoms using the 6-31G (d) basis set and Pt atoms using the LANL2DZ basis set.
Experimental data and analysis:
the electrochemical properties and energy comparison of each energy level of the tetracyclic metal platinum (II) complex phosphorescent light-emitting material are shown in the following table.
Table one: electrochemical property and energy comparison of individual energy level of quadridentate ring metal platinum (II) complex phosphorescent luminescent material
Figure BDA0002490096230000201
aHOMO＝-(EOxidation by oxygen+4.8)eV；bLUMO＝-(EReduction of+4.8)eV；cΔEg＝LUMO-HOMO。dExcited triplet energy level (E)T1) Calculated according to the phosphorescence emission spectrum of the corresponding luminescent material at low temperature (77K) in the 2-methyl tetrahydrofuran solution.
As shown in Table I, Pt (bp-1), Pt (bp-2) and Pt (bp-3) have similar HOMO orbital levels (-5.12eV to-5.14 eV), but have a large difference in LUMO orbital levels (-2.20eV to-2.40 eV); this result is also supported by Density Functional Theory (DFT) calculations (FIG. 2), and the HOMO orbital distributions of the three materials are very similar, both on the biphenyl portion and on the central Pt (II), but the LUMO orbital distributions are very different. This data demonstrates that the LUMO orbital level of a light emitting material can be efficiently tuned by adjusting the structure of the material ligand.
Meanwhile, as can be seen from Table one, although Pt (bp-3), Pt (bp-4) and Pt (bp-5) have the same ligand parent body and only have different substituents on the benzene ring, the HOMO orbital levels thereof are greatly different (-5.05eV to-5.27 eV); the result is also densityWith the support of functional theory (DFT) calculation (attached figures 3 and 4), as can be seen from comparison of electrostatic potential energy graphs of Pt (bp-4) and Pt (bp-5) in the attached figure 4, electron cloud density on central Pt (II) can be obviously increased by an electron donating substituent group (tBu), and the increase of negative charge is proved; electron withdrawing substituent (CF)3) The opposite is true. The result shows that the HOMO orbital level of the luminescent material can be efficiently regulated and controlled by adjusting the substituent on the material ligand.
The physical property data of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material are shown in the following table II:
table two: list of photophysical property data of quadridentate ring metal platinum (II) complex phosphorescent light-emitting material
Figure BDA0002490096230000211
Note: DCM is dichloromethane; 2-MeTHF is 2-methyltetrahydrofuran; PMMA is polymethyl methacrylate. λ is the wavelength; lambda [ alpha ]maxIs the maximum wavelength; tau is the excited state life of the material; phiPLIs the phosphorescence quantum efficiency.
As can be seen from the data in Table II: first, the emission wavelength of the platinum (II) complex phosphorescent light-emitting material is in the green light range under various environments, and the platinum (II) complex phosphorescent light-emitting material is a good green light-emitting material. Secondly, the luminescent materials all have short excited state lifetime (tau), especially the excited state lifetime (tau) in dichloromethane solution or polymethyl methacrylate film at room temperature is below 10 mus, and as can be seen from the attached fig. 12 and 13, the excited state lifetime is short by comparing the transient attenuation spectra obtained by the metal platinum (II) phosphorescent luminescent materials Pt (bp-1), Pt (bp-2), Pt (bp-3), Pt (bp-4) and Pt (bp-5) in 2-methyltetrahydrofuran at low temperature (77K), dichloromethane at room temperature and polymethyl methacrylate at room temperature. The short excited state lifetime is beneficial to the improvement of response speed of OLED devices as light emitting materials, and also beneficial to the improvement of phosphorescence efficiency. Thirdly, the platinum (II) complex phosphorescence luminescent material has high phosphorescence quantum efficiency which can reach more than 50% in dichloromethane solution or polymethyl methacrylate film at room temperature, which shows that the material can be used as phosphorescence luminescent material of OLED deviceA material. Fourthly, the maximum emission wavelength (lambda) of the platinum (II) complex phosphorescent luminescent material under different environments and conditionsmax) The shifts are small, and it can be seen from FIGS. 7 to 11 that the emission spectra obtained for the platinum (II) phosphorescent materials Pt (bp-1), Pt (bp-2), Pt (bp-3), Pt (bp-4) and Pt (bp-5) in 2-methyltetrahydrofuran at low temperature (77K), dichloromethane at room temperature and polymethylmethacrylate at room temperature are compared with each other, and lambda ismaxVery small shifts, especially of Pt (bp-2) < lambda >maxThe material is completely unchanged (figure 8), and the material has high luminous color stability.
FIG. 5 is a comparison of absorption spectra of Pt (bp-1), Pt (bp-2), Pt (bp-3), Pt (bp-4) and Pt (bp-5); FIG. 6 is a comparison of the absorption spectra of Pt (bp-1), Pt (bp-5) and their ligands.
As shown in the figure 14, the light stability of the phosphorescent material 5% Pt (bp-2) polystyrene film and 5% PtON1 polystyrene film under the excitation of 375nm ultraviolet light (light intensity: 500W/m2) is compared, and the light stability of Pt (bp-2) is far higher than that of PtON1 containing a five-membered heterocyclic ring linked with an oxygen atom. The light stability comparison data shows that the material molecular design strategy developed in the application of the invention is that the light stability of the platinum (II) complex phosphorescence luminescent material can be effectively improved by adopting the ligand which is linked by nitrogen atoms and only contains the benzene ring structure unit and the pyridine ring structure unit with stable structures.
The experimental data and theoretical calculation results fully indicate that the quadridentate ring metal platinum (II) complex phosphorescent light-emitting material which is developed in the application and is based on nitrogen atom linkage and only contains benzene ring and pyridine ring has the characteristics of easily adjustable HOMO and LUMO orbital energy levels, short excited state life, high phosphorescent quantum efficiency, good light-emitting color stability and strong material light stability, and has great application prospect in the OLED field.
The invention relates to application of a four-tooth ring metal platinum (II) phosphorescent light-emitting material in a light-emitting layer of an organic electroluminescent device. In an organic light-emitting element, carriers are injected into a light-emitting material from both positive and negative electrodes, and the light-emitting material in an excited state is generated and emits light. The complex of the present invention represented by the general formula (1) can be used as a phosphorescent material for an excellent organic light-emitting device such as an organic photoluminescent device or an organic electroluminescent device. The organic photoluminescent element has a structure in which at least a light-emitting layer is formed over a substrate. The organic electroluminescent element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed. The organic layer may be composed of only the light-emitting layer, or may have 1 or more organic layers other than the light-emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function. Fig. 15 shows a schematic structure of a specific organic light-emitting element. In fig. 15, 7 layers are shown from bottom to top, and a substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode are sequentially shown, where the light-emitting layer is a mixed layer in which a guest material is doped with a host material.
The compounds represented in examples 1 to 5 were applied as phosphorescent light emitting materials to OLED devices, and the structures are represented as:
ITO/HATCN (10nm)/TAPC (65nm)/CBP the compounds represented in examples 1-5 (10-20 wt.%, 20nm)/Bepp2(10nm)/Li2CO3:Bepp2(5％,30nm)/Li2CO3(1nm)/Al(100nm)
Wherein, the ITO is a transparent anode; HATCN is a hole-injecting layer, TCTA is a hole-transporting layer, CBP is a host material, the compounds represented in examples 1 to 5 (10 to 20 wt.% is a doping concentration, 20nm is a thickness of a light-emitting layer) are guest materials, Bepp2As electron transport layer, Li2CO3Is an electron injection layer and Al is a cathode. The number in parentheses in nanometers (nm) is the thickness of the film.
It should be noted that the structure is an example of an application of the light emitting material of the present invention, and does not constitute a limitation of the structure of the specific OLED device of the light emitting material of the present invention, and the phosphorescent light emitting material is not limited to the compounds shown in examples 1 to 5.
The molecular formula of the applied material in the device is as follows:
Figure BDA0002490096230000231
it will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice. For example, many of the substituent structures described herein may be substituted with other structures without departing from the spirit of the invention.

Claims (10)

1. A quadridentate ring metal platinum complex phosphorescent material is characterized in that the chemical formula is shown as a general formula (1),
Figure FDA0002490096220000011
wherein R is11、R12、R21、R22、R23、R24、R25、R26、R31、R32、R33、R34、R35And R36Each independently represents a hydrogen atom or a substituent, R11、R12、R21、R22、R23、R24、R25、R26、R31、R32、R33、R34、R35And R36Two or more of which may be joined to form a fused ring, which may also be fused with other rings.
2. The tetradentate ring metal platinum complex phosphorescent material of claim 1, wherein the substituent is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and a 5-to 7-membered heterocyclic group.
3. The tetradentate ring metal platinum complex phosphorescent material as claimed in claim 1, wherein R of the general formula (1)11、R12At least one of which is a benzene ring.
4. The tetradentate ring metal platinum complex phosphorescent material as claimed in claim 1, wherein R of the general formula (1)11And R12Are the same substituents.
5. The tetradentate ring metal platinum complex phosphorescent material as claimed in claim 1, wherein R of the general formula (1)21、R22、R23At least two of which are hydrogen atoms, R24、R25、R26At least two of which are hydrogen atoms, R31、R32、R33At least two of which are hydrogen atoms, R34、R35、R36At least two of which are hydrogen atoms.
6. The tetraadentate ring metal platinum complex phosphorescent material as described in claim 1, wherein the general formula (1) is specifically a compound represented by the following general formula (2),
Figure FDA0002490096220000021
wherein A is1、A2At least one of them represents a single bond or a divalent linking group, A3、A4At least one of them represents a single bond or a divalent linking group; the divalent linking group is independently selected from the group consisting of: -CR1aR2a-、-CR1aR2a-CR3aR4a-、-CR1aR2a-CR3aR4a-CR5aR6a-、-CR1aR2a-NR3a-、-CR1a＝CR2a-CR3aR4a-、-O-SiR1aR2a-、-CRlaR2a-S-、-CR1aR2a-O-and-C-SiR1aR2a-, wherein each R1aTo R6aAre the same or different and are independently selected from hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, or combinations thereof; any adjacent R1aTo R6aOptionally linked to form a saturated five-membered ring or a saturated six-membered ring; r22、R23、R24、R25、R32、R33、R34、R35、R41、R42、R43、R44、R45And R46Each independently represents a hydrogen atom or a substituent.
7. The tetradentate ring metal platinum complex phosphorescent material as claimed in claim 6, wherein A of the general formula (2)1、A2One of (1), and A3、A4One of which is provided with the same divalent linking group.
8. The tetraadentate ring metal platinum complex phosphorescent material as claimed in claim 6, wherein the general formula (2) is specifically a compound represented by the following general formula (3),
Figure FDA0002490096220000022
wherein A is3、A4At least one of them represents a single bond or a divalent linking group; the divalent linking group is independently selected from the group consisting of: -CR1aR2a-、-CR1aR2a-CR3aR4a-、-CR1aR2a-CR3aR4a-CR5aR6a-、-CR1aR2a-NR3a-、-CR1a＝CR2a-CR3aR4a-、-O-SiR1aR2a-、-CRlaR2a-S-、-CR1aR2a-O-and-C-SiR1aR2a-, wherein each R1aTo R6aAre the same or different and are independently selected from hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, or combinations thereof; any adjacent R1aTo R6aOptionally linked to form a saturated five-membered ring or a saturated six-membered ring; r35Represents a hydrogen atom or a substituent.
9. The tetradentate ring metal platinum complex phosphorescent material as claimed in claim 1, wherein the phosphorescent material is any one of the following structural formulas,
Figure FDA0002490096220000031
10. an organic light-emitting element characterized by having a light-emitting layer containing the tetradentate ring metal platinum complex phosphorescent material described in any one of claims 1 to 9 on a substrate.
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