CN113105509A - Complex phosphorescent material based on electron-deficient functional group - Google Patents
Complex phosphorescent material based on electron-deficient functional group Download PDFInfo
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- 230000031700 light absorption Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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Abstract
The complex phosphorescent material based on the electron-deficient functional group has a molecular skeleton general formula as follows:
r is an electron-deficient substituent;
Description
Technical Field
The invention relates to the technical field of organic luminescence, in particular to a complex phosphorescent material based on electron-deficient functional groups.
Background
The organic metal platinum complex phosphorescent material has great application value in the fields of solar cells, organic synthesis catalysis, photolysis water catalysis, cell detection, targeted cancer treatment, organic light-emitting diodes and the like. The light absorption capacity and the light emitting capacity of the complex are one of the most important parameters for determining the application value of the complex; meanwhile, the redox ability of the complex has an important influence on the carrier transport property. These properties are very interesting control points in current research, and commonly adopted means include changing the number of teeth of the cyclometalated ligand, such as changing from a bidentate ligand to a tridentate or tetradentate ligand, and changing the type of ancillary ligand, such as changing from acetylacetone to picolinic acid, etc. The measures can influence the lowest excited state energy level and the electrochemical property of the organic metal platinum complex, thereby achieving the aim of optimizing the property of the complex. The spin-orbit coupling effect inherent in the organometallic platinum complex is not only related to the lowest excited state but also to the excited state of higher energy level. However, there is currently little interest in higher-level excited states. How to regulate and control the position of a higher-energy-level excited state through molecular structure design, more precisely, how to make the higher-energy-level excited state slightly higher than the lowest excited state so as to facilitate the coupling effect between the higher-energy-level excited state and the lowest excited state, further enhance the light absorption capacity and the light emitting capacity of the complex and realize the comprehensive optimization of the performance of the complex, which is an important problem to be solved at present.
Disclosure of Invention
In order to solve the problems, a wider space is provided for the performance regulation of the organic metal platinum complex, and a functionalized phosphorescent material with more excellent performance is obtained, the invention aims to disclose a complex phosphorescent material based on electron-deficient functional groups, the complex takes a tetradentate ligand as a main ring metal ligand, the luminescent color of the complex is determined, and the spin-orbit coupling effect of the complex is enhanced by coordination with two metal centers simultaneously, so that the leap rate between the complexes is increased; the electron-deficient functional group is used for regulating and controlling the position of a high-energy-level excited state of the complex and promoting the interaction of the complex and a lowest excited state.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the complex phosphorescent material based on the electron-deficient functional group has a molecular skeleton general formula as follows:
in the general formula of the molecular skeleton, R is an electron-deficient substituent group and comprises any one of the following organic groups:
Compared with the traditional platinum complex, the complex phosphorescent material based on the electron-deficient functional group has the following obvious improvements:
firstly, the luminescent color purity is high, which is beneficial to showing more excellent display effect; the yellow light-emitting material prepared by the invention has the color coordinates of (0.45,0.54), and belongs to yellow light with high color purity;
secondly, the quantum efficiency is obviously improved, which is beneficial to obviously enhancing the electroluminescent capability; the luminous efficiency of the luminescent material prepared by the invention is as high as 85-96%;
thirdly, the oxidation reduction property is improved, and the carrier injection transmission property is favorably optimized; the luminescent material prepared by the invention has very low oxidation-reduction potential in cyclic voltammetry, and the oxidation-reduction potential is only 0.13V to 0.19V;
fourthly, the solubility is enhanced, which is beneficial to applying the composite material by adopting various different processing and using methods; the luminescent material prepared by the invention can be effectively dissolved in solvents such as dichloromethane, chlorobenzene, chloroform and the like, and can be processed by a solution spin coating method to prepare the luminescent material into a luminescent film.
Drawings
FIG. 1 is a schematic representation of the synthesis of various classes of organic ligands according to the present invention.
FIG. 2 is a schematic diagram of the synthesis of phosphorescent complexes based on electron deficient functional groups according to the present invention.
FIG. 3 is a luminescence diagram of a phosphorescent complex Pt1 based on an electron-deficient functional group.
FIG. 4 is a luminescence diagram of a phosphorescent complex Pt2 based on an electron-deficient functional group.
FIG. 5 is a luminescence diagram of a phosphorescent complex Pt3 based on an electron-deficient functional group.
FIG. 6 is a luminescence diagram of a phosphorescent complex Pt4 based on an electron-deficient functional group.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
The technical scheme of the phosphorescent complex based on the electron-deficient functional group is as follows.
The general formula of the molecular skeleton is as follows:
in the general formula of the molecular skeleton, R is a key electron-deficient substituent group and comprises any one of the following organic groups:
The synthesis of the phosphorescent complex based on the electron-deficient functional group comprises synthesis of a ligand and synthesis of the complex.
Based on the electron-deficient functional group ligand, the synthesis steps are as follows:
mixing an electron-deficient functional group compound and a tetradentate precursor according to the mass ratio of 1: 1 into a reaction vessel to which 0.05% equivalent of tetrakis (triphenylphosphine palladium) catalyst, 50 ml of tetrahydrofuran and 30ml of 2m concentration were added under nitrogen atmosphereHeating to 110 ℃ in a nitrogen atmosphere for reacting overnight; stopping heating, cooling to room temperature, adding deionized water into the reaction mixed solution, and extracting the reaction mixture by using dichloromethane; drying the obtained organic phase by using anhydrous sodium sulfate, concentrating, separating and purifying by using a silica gel column to obtain the corresponding ligand based on the electron-deficient functional group
The phosphorescent complex based on the electron-deficient functional group comprises the following synthetic steps:
will be based on electron deficient functional group ligands
And K2PtCl4According to the amount of substance 1: 2.1, adding a mixed solvent of ethylene glycol ethyl ether and water into a reaction container in a volume ratio of 3: 1, heating to 90 ℃ in a nitrogen atmosphere for reaction for 4 hours; stopping heating, cooling to room temperature, adding deionized water into the reaction mixed solution, separating out solids, filtering and drying the separated solids; mixing the dried solid with acetylacetone (acac) ligand and anhydrous sodium carbonate, wherein the mass ratio of the materials is 1: 3: 10, adding the mixture into ethylene glycol ethyl ether, heating the mixture to 110 ℃ in a nitrogen atmosphere, and reacting for 12 hours to obtain the corresponding target organic metal platinum complex.
Example one
The ligand L-1 based on electron-deficient functional groups has the structural formula
Referring to fig. 1, the synthesis method comprises: 1 equivalent of electron-deficient functional group compound
And 1 equivalent of a tetradentate precursor
Charging into a reaction vessel under nitrogen atmosphereAdding 0.05 percent equivalent of a tetrakis (triphenylphosphine palladium) catalyst, 50 ml of tetrahydrofuran and 30ml of potassium carbonate solution with the concentration of 2mol/L into the reaction vessel, and heating to 110 ℃ in a nitrogen atmosphere for reacting overnight; the heating was stopped, after cooling to room temperature, deionized water was added to the reaction mixture solution, and the reaction mixture was extracted with dichloromethane. And drying the obtained organic phase by using anhydrous sodium sulfate, concentrating, separating and purifying by using a silica gel column to obtain the corresponding ligand L-1 based on the electron-deficient functional group. The nuclear magnetic characterization data are:1H NMR(400MHz,CDCl3,δ):8.66(d,J＝4.8Hz,2H),7.92(d,J＝8.8Hz,4H),7.74-7.69(m,12H),7.58-7.46(m,8H),7.27-7.24(m,6H),7.20(t,J＝5.6Hz,2H)。
the phosphorescence complex Pt1 based on electron-deficient functional group has the structural formula
Referring to fig. 2, the synthesis method comprises: will be based on electron deficient functional group ligands
And K2PtCl4According to the amount of substance 1: 2.1, adding 40 ml of mixed solvent (volume ratio is 3: 1) of ethylene glycol ether and water into a reaction container under the nitrogen atmosphere, and heating to 90 ℃ under the nitrogen atmosphere for reaction for 4 hours; stopping heating, cooling to room temperature, adding deionized water into the reaction mixed solution, separating out solids, filtering and drying the separated solids; mixing the dried solid with acetylacetone (acac) ligand and anhydrous sodium carbonate according to the mass ratio of 1: 3: 10 is added into 40 ml of ethylene glycol ethyl ether, and the mixture is heated to 110 ℃ in a nitrogen atmosphere to react for 12 hours; after the reaction is finished, pouring the reaction mixture into 30mL of deionized water to separate out colored solids; after the solid is filtered and dried, the solid is separated and purified by silica gel, and finally the phosphorescence complex Pt1 based on the electron-deficient functional group is obtained. The nuclear magnetic characterization data are:1H NMR(400MHz,CDCl3,δ):8.90(d,J＝5.6Hz,2H),7.75-7.65(m,10H),7.57-7.46(m,10H),7.38-7.33(m,6H),7.02(t,J＝6.4Hz,2H),6.92(dd,J＝6.4,8.4Hz,2H),5.38(s,2H),1.96(s,6H),1.73(s,6H)。
example two
The structural formula of the ligand L-2 based on the electron-deficient functional group is shown in the specification
Referring to fig. 1, the synthesis method comprises: 1 equivalent of electron-deficient functional group compound
And 1 equivalent of a tetradentate precursor
Putting the mixture into a reaction vessel, adding 0.05 percent equivalent of tetrakis (triphenylphosphine palladium) catalyst, 50 ml of tetrahydrofuran and 30ml of 2mol/L potassium carbonate solution into the reaction vessel under the nitrogen atmosphere, and heating the mixture to 110 ℃ under the nitrogen atmosphere for reacting overnight; stopping heating, cooling to room temperature, adding deionized water into the reaction mixed solution, and extracting the reaction mixture by using dichloromethane; and drying the obtained organic phase by using anhydrous sodium sulfate, concentrating, separating and purifying by using a silica gel column to obtain the corresponding ligand L-2 based on the electron-deficient functional group. The nuclear magnetic characterization data are:1H NMR(400MHz,CDCl3,δ):8.67(d,J＝4.4Hz,2H),7.98(d,J＝7.2Hz,4H),7.93(d,J＝8.4Hz,4H),7.76-7.69(m,6H),7.58-7.48(m,6H),7.26-7.12(m,7H)。
the structural formula of the phosphorescence complex Pt2 based on electron-deficient functional groups is shown in the specification
Referring to fig. 2, the synthesis method comprises: will be based on electron deficient functional group ligands
And K2PtCl4According to the amount of substance 1: 2.1, adding 40 ml of mixed solvent (volume ratio is 3: 1) of ethylene glycol ether and water into a reaction container under the nitrogen atmosphere, and heating to 90 ℃ under the nitrogen atmosphere for reaction for 4 hours; stopping heating and coolingAdding deionized water into the reaction mixed solution after the temperature is reduced to room temperature, separating out solids, filtering and drying the separated solids; mixing the dried solid with acetylacetone (acac) ligand and anhydrous sodium carbonate according to the mass ratio of 1: 3: 10 is added into 40 ml of ethylene glycol ethyl ether, and the mixture is heated to 110 ℃ in a nitrogen atmosphere to react for 12 hours; after the reaction is finished, pouring the reaction mixture into 30mL of deionized water to separate out colored solids; after the solid is filtered and dried, the solid is separated and purified by silica gel, and finally the phosphorescence complex Pt2 based on the electron-deficient functional group is obtained. The nuclear magnetic characterization data are:1H NMR(400MHz,CDCl3,δ):8.93(d,J＝5.6Hz,2H),8.01-7.98(m,4H),7.77(t,J＝7.6Hz,2H),7.70(d,J＝8.4Hz,2H),7.60-7.50(m,7H),7.39-7.35(m,6H),7.05(t,J＝6.4Hz,2H),6.93(d,J＝8.0Hz,2H),5.40(s,2H),1.99(s,6H),1.75(s,6H)。
EXAMPLE III
The structural formula of the ligand L-3 based on the electron-deficient functional group is shown in the specification
Referring to fig. 1, the synthesis method comprises: 1 equivalent of electron-deficient functional group compound
And 1 equivalent of a tetradentate precursor
Putting the mixture into a reaction vessel, adding 0.05 percent equivalent of tetrakis (triphenylphosphine palladium) catalyst, 50 ml of tetrahydrofuran and 30ml of 2mol/L potassium carbonate solution into the reaction vessel under the nitrogen atmosphere, and heating the mixture to 110 ℃ under the nitrogen atmosphere for reacting overnight; stopping heating, cooling to room temperature, adding deionized water into the reaction mixed solution, and extracting the reaction mixture by using dichloromethane; and drying the obtained organic phase by using anhydrous sodium sulfate, concentrating, separating and purifying by using a silica gel column to obtain the corresponding ligand L-3 based on the electron-deficient functional group. The nuclear magnetic characterization data are:1H NMR(400MHz,CDCl3,δ):8.67(d,J＝4.4Hz,3H),7.92(d,J＝8.4Hz,6H),7.75–7.69(m,6H),7.27(d,J＝8.4Hz,6H),7.20(t,J＝5.6Hz,3H)。
the structural formula of the phosphorescence complex Pt3 based on electron-deficient functional groups is shown in the specification
Referring to fig. 2, the synthesis method comprises: will be based on electron deficient functional group ligands
And K2PtCl4According to the amount of substance 1: 2.1, adding 40 ml of mixed solvent (volume ratio is 3: 1) of ethylene glycol ethyl ether and water into a reaction container under nitrogen atmosphere, heating to 90 ℃ and reacting for 4 hours; stopping heating, cooling to room temperature, adding deionized water into the reaction mixed solution, separating out solids, filtering and drying the separated solids; mixing the dried solid with acetylacetone (acac) ligand and anhydrous sodium carbonate according to the mass ratio of 1: 3: 10 is added into 40 ml of ethylene glycol ethyl ether, and the mixture is heated to 110 ℃ in a nitrogen atmosphere to react for 12 hours; after the reaction is finished, pouring the reaction mixture into 30mL of deionized water to separate out colored solids; after the solid is filtered and dried, the solid is separated and purified by silica gel, and finally the phosphorescence complex Pt3 based on the electron-deficient functional group is obtained. The nuclear magnetic characterization data are:1H NMR(400MHz,CDCl3,δ):8.89(d,J＝5.6Hz,2H),8.64(d,J＝4.8Hz,1H),7.90(d,J＝8.4Hz,2H),7.73–7.67(m,4H),7.49(d,J＝8.0Hz,2H),7.39(d,J＝2.0Hz,2H),7.36–7.32(m,4H),7.17–7.14(m,1H),7.00(t,J＝6.4Hz,2H),6.90(dd,J＝8.4,2.0Hz,2H),5.36(s,2H),1.95(s,6H),1.72(s,6H)。
example four
The structural formula of the ligand L-4 based on the electron-deficient functional group is shown in the specification
Referring to fig. 1, the synthesis method comprises: 1 equivalent of electron-deficient functional group compound
And 1 equivalent of a tetradentate precursor
Putting the mixture into a reaction vessel, adding 0.05 percent equivalent of tetrakis (triphenylphosphine palladium) catalyst, 50 ml of tetrahydrofuran and 30ml of 2mol/L potassium carbonate solution into the reaction vessel under the nitrogen atmosphere, and heating the mixture to 110 ℃ under the nitrogen atmosphere for reacting overnight; stopping heating, cooling to room temperature, adding deionized water into the reaction mixed solution, and extracting the reaction mixture by using dichloromethane; and drying the obtained organic phase by using anhydrous sodium sulfate, concentrating, separating and purifying by using a silica gel column to obtain the corresponding ligand L-4 based on the electron-deficient functional group. The nuclear magnetic characterization data are:1H NMR(400MHz,CDCl3,δ):8.69(d,J＝4.4Hz,2H),7.95(d,J＝8.8Hz,4H),7.78-7.71(m,4H),7.63-7.61(m,6H),7.29-7.26(m,6H),7.22(t,J＝5.6Hz,2H),6.86(s,4H),2.34(s,6H),2.07(s,12H)。
the structural formula of the phosphorescence complex Pt4 based on electron-deficient functional groups is shown in the specification
Referring to the attached figure 2, the synthesis method comprises the following steps: will be based on electron deficient functional group ligands
And K2PtCl4According to the amount of substance 1: 2.1, adding 40 ml of mixed solvent (volume ratio is 3: 1) of ethylene glycol ether and water into a reaction container under the nitrogen atmosphere, and heating to 90 ℃ under the nitrogen atmosphere for reaction for 4 hours; stopping heating, cooling to room temperature, adding deionized water into the reaction mixed solution, separating out solids, filtering and drying the separated solids; mixing the dried solid with acetylacetone (acac) ligand and anhydrous sodium carbonate according to the mass ratio of 1: 3: 10 is added into 40 ml of ethylene glycol ethyl ether, and the mixture is heated to 110 ℃ in a nitrogen atmosphere to react for 12 hours; after the reaction is finished, pouring the reaction mixture into 30mL of deionized water to separate out colored solids; after the solid is filtered and dried, the solid is separated and purified by silica gel, and finally the phosphorescence complex Pt4 based on the electron-deficient functional group is obtained. Nuclear magnetic characterization numberAccording to the following steps:1H NMR(400MHz,CDCl3,δ):8.90(d,J＝5.2Hz,2H),7.73(t,J＝7.2Hz,2H),7.58-7.56(m,6H),7.49(d,J＝8.0Hz,2H),7.38-7.32(m,6H),7.01(t,J＝6.0Hz,2H),6.92(dd,J＝6.0,8.4Hz,2H),6.83(s,4H),5.38(s,2H),2.32(s,6H),2.04(s,12H),1.96(s,6H),1.74(s,6H)。
the organic ligand based on electron-deficient functional groups and the related phosphorescent complex prepared by the invention have better solubility in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and the like, are beneficial to preparing an organic film with good appearance by a solution method, and enrich the processing and application means of materials. Doping the obtained material into a main material, and testing the luminous efficiency of the material, wherein the luminous quantum efficiency of the organic ligand is between 60% and 93%; the luminescence quantum efficiency of the platinum complex exceeds 85 percent, and reaches 96 percent at most. The luminescence spectra of complexes Pt1, Pt2, Pt3, and Pt4 are shown in FIGS. 3-6, respectively. The introduction of the electron-deficient group effectively changes the carrier transmission behavior of the luminescent material, and has obvious positive effect on improving the performance of related electronic devices. In addition, the yellow light-emitting material prepared by the invention has the color coordinates of (0.45,0.54), belongs to yellow light with high color purity, and is favorable for improving the electroluminescent display quality. In a word, due to the existence of electron-deficient groups, various key physical properties of the luminescent material are comprehensively optimized, and the application value of the luminescent material in the fields of electroluminescence, imaging detection, photocatalysis and the like is improved.
While the invention has been described in connection with specific embodiments thereof, it will be understood that these should not be construed as limiting the scope of the invention, which is defined in the following claims, and any variations which fall within the scope of the claims are intended to be embraced thereby.
Claims (5)
1. The complex phosphorescent light-emitting material based on the electron-deficient functional group is characterized in that the molecular skeleton general formula is as follows:
in the general formula of the molecular skeleton, R is an electron-deficient substituent group and comprises any one of the following organic groups:
2. The complex phosphorescent light-emitting material based on the electron-deficient functional group according to claim 1, wherein the molecular skeleton formula is as follows:
3. the complex phosphorescent light-emitting material based on the electron-deficient functional group according to claim 1, wherein the molecular skeleton formula is as follows:
4. the complex phosphorescent light-emitting material based on the electron-deficient functional group according to claim 1, wherein the molecular skeleton formula is as follows:
5. the electron-deficient functional group according to claim 1The complex phosphorescence luminescent material is characterized in that the molecular skeleton general formula is as follows:
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