CN110818738B - Thermally activated delayed fluorescence material based on ether bond conformation locking triphenylphosphine oxide receptor - Google Patents

Thermally activated delayed fluorescence material based on ether bond conformation locking triphenylphosphine oxide receptor Download PDF

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CN110818738B
CN110818738B CN201911157871.3A CN201911157871A CN110818738B CN 110818738 B CN110818738 B CN 110818738B CN 201911157871 A CN201911157871 A CN 201911157871A CN 110818738 B CN110818738 B CN 110818738B
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周桂江
宋东东
杨晓龙
张引弟
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Xian Jiaotong University
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Abstract

A thermally activated delayed fluorescence material based on the conformational locking of triphenylphosphine oxide receptors, having a structure represented by the formula:

Description

Thermally activated delayed fluorescence material based on ether bond conformation locking triphenylphosphine oxide receptor
Technical Field
The invention relates to the technical field of organic photoelectric new materials, in particular to a thermal activation delay fluorescent material based on ether bond conformation locking triphenylphosphine oxide receptor.
Background
Compared with the traditional light-emitting technology, the organic light-emitting technology has the advantages of self-luminescence, wide viewing angle, high contrast, low energy consumption, high response speed and the like. The organic luminescent material can directly convert electric energy into light, and has important development and application prospects for large-area flexible display and lighting devices which are urgently needed at present. The excellent organic electroluminescent material plays a decisive role in the organic electroluminescent device (OLED) in light-emitting quantum efficiency, color purity, charge injection and transmission capacity and the like. In conventional first generation fluorescent emission materials, the Internal Quantum Efficiency (IQE) is only 25%; while the second generation phosphorescence emission material based on noble metal can reach 100 percent of IQE, the problems of higher synthesis cost, higher preparation difficulty of deep blue light material and the like still exist. Whereas Thermally Activated Delayed Fluorescence (TADF) materials can increase the External Quantum Efficiency (EQE) to 20% -30% by utilizing the intersystem crossing of triplet excitons, comparable to phosphorescent materials. Has great development potential for replacing expensive noble metal phosphorescence materials. The thermal activation delay fluorescent material based on the ether bond conformation locking triphenylphosphine oxide receptor has better chemical stability and electron affinity due to a better rigid structure. Meanwhile, the non-radiative transition process of the luminescent material can be effectively inhibited, so that the luminescent performance is improved. And is therefore highly welcomed by a large number of researchers. But molecular designs based on this group lack diversity.
Disclosure of Invention
In order to effectively overcome the defects in the prior art, the invention aims to provide a thermal activation delayed fluorescence material based on ether bond conformation locking triphenylphosphine oxide acceptor, which has excellent performance on the key performances of luminescent color purity, quantum efficiency and charge injection and transmission capacity.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
a thermally activated delayed fluorescence material based on the conformational locking of triphenylphosphine oxide receptors, having a structure represented by the formula:
Figure BDA0002285295410000021
in the middle of
R 1 Represents a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted triphenylamino group, a substituted or unsubstituted diphenylboron group;
R 1 has a structure selected from one of the following:
Figure BDA0002285295410000031
R 2 represents a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted spirosilafluorenyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group,Substituted or unsubstituted fluorenyl, substituted or unsubstituted acridinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted thienyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted anthryl, substituted or unsubstituted triphenylamino, substituted or unsubstituted diphenylboron;
R 2 has a structure selected from one of the following:
Figure BDA0002285295410000041
R 3 represents a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted triphenylamino group, a substituted or unsubstituted diphenylboron group;
R 3 has a structure selected from one of the following:
Figure BDA0002285295410000051
R 4 represents a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted triphenylamino group, a substituted or unsubstituted diphenylboron group;
R 4 has a structure selected from one of the following:
Figure BDA0002285295410000061
r in the same molecule 2 、R 3 May be identical or different.
Compared with the structure and the property of the existing thermal delay fluorescent material, the invention has the following two most obvious innovation points and advancement:
the first, the invention synthesizes the thermal activation delay fluorescent material to lock the cyclic triphenylphosphine oxide with ether bond conformation as the core, it has two functions: 1. the rigidity of the luminous molecular core is obviously enhanced, the non-radiative transition process of the molecules caused by the vibration or rotation of the core can be inhibited, and the luminous efficiency of the material is improved; 2. the cyclic triphenylphosphine oxide locked by the ether bond conformation has the characteristic of strong electron attraction, can help to enhance the injection and transmission capacity of the luminescent material to electrons, and effectively reduces the working voltage of the organic electroluminescent device.
Second, the material has excellent performance in several key properties of luminous color purity, quantum efficiency and charge injection and transmission capability.
From the aspect of molecular structure, the molecular skeleton obtained by the invention has stronger rigidity and novel structure; from the aspect of material performance, the material synthesized by the invention has excellent luminous performance.
Drawings
FIG. 1 is a route diagram of a thermally retarded fluorescence luminescent material DOPNA-O, DOPNA-S, DOPNA-2O, DOPNA-2S, DOPNA-m-O, DOPNA-m-S, DOPNA-m-2O, DOPNA-m-2S, DOPNA-p-O synthesized in accordance with the present invention.
FIG. 2 is a luminescence spectrum of a thermal delay fluorescent luminescent material DOPNA-O, DOPNA-S, DOPNA-2O, DOPNA-2S, DOPNA-m-O, DOPNA-m-S, DOPNA-m-2O, DOPNA-m-2S, DOPNA-p-O synthesized according to the present invention.
FIG. 3 shows the life cycle decay curve of the thermal delay fluorescent luminescent material DOPNA-O, DOPNA-2O, DOPNA-m-O, DOPNA-m-2O, DOPNA-p-O synthesized according to the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of the present invention will be made with reference to examples. In the various embodiments of the present invention, numerous technical details are set forth in order to provide a better understanding of the present invention. However, the technical solutions claimed in the claims of the present invention can be realized without these technical details and various changes and modifications based on the following embodiments.
Example 1
Eight luminescent materials (para/di-para substitution) were synthesized in this example, DOPNA-O, DOPNA-S, DOPNA-2O, DOPNA-2S, DOPNA-m-O, DOPNA-m-S, DOPNA-m-2O, DOPNA-m-2S, respectively, having the structural formulas:
Figure BDA0002285295410000081
referring to fig. 1, the synthesis method of the above eight materials is as follows.
Phenol, 1, 3-dibromobenzene, o-iodophenol, 2, 6-difluoro-4-bromoiodobenzene, p-bromoiodobenzene, m-bromoiodobenzene, phenothiazine, phenoxazine, all are commercially available.
First step, 1, 3-diphenoxybenzene synthesis
1, 3-dibromobenzene (5.0 g,20.0 mmol), phenol (5.2 g,60.0 mmol), cesium carbonate (20.7 g,60.0 mmol) and cuprous bromide (0.91 g,6.0 mmol) were dissolved together in 35mL of NMP (N-methylpyrrolidone) solution under nitrogen atmosphere, and reacted at 160℃for 12 hours; after the reaction is finished, pouring ice water, extracting with petroleum ether for three times, drying with anhydrous sodium sulfate, spin drying, separating petroleum ether by column chromatography with eluent to obtain 4.1g of oil-free substance with a yield of 72%; 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.32(t,J＝8.0Hz,4H),7.23(t,J＝8.0Hz,1H),7.10(t,J＝7.6Hz,2H),7.02(d,J＝8.0Hz,4H),6.72–6.69(m,3H). 13 C NMR(100MHz,CDCl 3 ):δ(ppm)160.3,158.3,132.0,131.5,125.3,120.8,114.8,110.9；
and a second step of: synthesis of OBr/SBr/m-OBr/m-SBr
Phenothiazine (2.0 g,10.9 mmol), p-bromoiodobenzene (2.8 g,10.0 mmol) and copper powder (3 g,23.4 mmol) were dissolved together in 30mL of DMF (N-N-dimethylformamide) under nitrogen and reacted at 160℃for 48h. After the reaction is finished, adding ice water, carrying out suction filtration, extracting filter residues with a dichloromethane solution for 3 times, dissolving, drying with anhydrous sodium sulfate, spin-drying, and carrying out dichloromethane: petroleum ether (v: v) =1:5 is used as a leaching agent for column chromatography separation to obtain white solid product SBr 2.5g, and the yield is 66%; if the starting material was replaced by phenoxazine and the other experimental procedures were the same as described above, a white solid product, OBr2.3g, was obtained with a yield of 68%. For m-SBr/m-OBr, m-bromoiodobenzene, phenothiazine and phenoxazine are respectively used as initial raw materials, and the rest experimental processes are the same as the above, and are not repeated here; finally, m-SBr 2.5g was obtained in 66% yield. m-OBr2.3g, yield 68%;
SBr
dichloromethane: petroleum ether (v: v) =1:5 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.70(d,J＝8.6Hz,2H),7.25(d,J＝8.6Hz,2H),7.04(dd,J＝7.3,1.8Hz,2H),6.86(m,4H),6.24(dd,J＝8.0,1.4Hz,2H). 13 C NMR(100MHz,CDCl 3 ):δ(ppm)144.2,143.8,140.9,133.8,131.9,129.7,129.5,122.5,122.2,121.2,117.5,116.2；
OBr
Dichloromethane: petroleum ether (v: v) =1:5 1 H NMR(400MHz,CDCl 3 ):δ(ppm)5.91(dd,J＝7.8,1.4Hz,2H),6.57–6.70(m,6H),7.23(d,J＝8.6Hz,2H),7.72(d,J＝8.6Hz,2H)； 13 C NMR(100MHz,CDCl 3 ):δ(ppm)113.3,115.7,121.7,122.5,123.4,132.9,134.1,134.6,138.2,144.0；
m-SBr
Dichloromethane: petroleum ether (v: v) =1:5 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.56(d,J＝8.8Hz,2H),7.44(t,J＝8.0Hz,1H),7.32(d,J＝7.6Hz,1H),7.19(d,J＝7.6Hz,2H),7.03-6.85(m,4H),6.36(d,J＝7.6Hz,2H)；
m-OBr
Dichloromethane: petroleum ether (v: v) =1:5 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.63-7.61(m,1H),7.54(s,1H),7.48(t,J＝5.2Hz,1H),7.31(d,J＝4.4Hz,1H),6.71-6.60(m,6H),5.92(d,J＝5.2Hz,2H)；
And a third step of: synthesis of OB/SB/m-OB/m-SB
SBr (1.0 g,2.8 mmol), pinacol diboronate (1.1 g,4.3 mmol), potassium acetate (0.93 g,9.48 mmol), pd (dppf) Cl under nitrogen 2 (0.18 g,0.63 mmol) in 20mL of 1, 4-dioxane solution, at 110deg.C for 12h; after the reaction is finished, extracting with dichloromethane for three times, drying with anhydrous sodium sulfate, spin-drying, and dichloromethane: petroleum ether (v: v) =1:3 was column chromatographed as a eluent to give product SB0.62g as a white solid in 53% yield. If the raw material is replaced by OBr, and other experimental steps are the same as the above, 0.65g of white solid product OB can be obtained, and the yield is 55%; for m-SB/m-OB, then m-SBr/m-OBr is used as the initial starting material, and the remainder of the experiment is the same as described above and will not be repeated here. Finally, m-SB0.62g was obtained in 53% yield. m-OB 0.65g, yield 55%.
SB
Dichloromethane: petroleum ether (v: v) =1:3 1 H NMR(400MHz,DMSO-d 6 ):δ(ppm)7.88(d,J＝8.3Hz,2H),7.35(d,J＝8.3Hz,2H),7.18(dd,J＝7.5,1.6Hz,2H),7.02(ddd,J＝7.9,7.7,1.7Hz,2H),6.95(ddd,J＝7.5,7.5,1.3Hz,2H),6.41(dd,J＝8.1,1.3Hz,2H),1.33(s,12H). 13 C NMR(100MHz,DMSO-d 6 ):δ(ppm)144.5,143.4,137.3,127.9,127.6,123.9,122.4,118.6,84.3,25.2；
OB
Dichloromethane: petroleum ether (v: v) =1:3 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.02(d,J＝8.0Hz,2H),7.35(d,J＝8.0Hz,2H),6.68(dd,J＝7.8Hz,1.4Hz,2H),6.63(t,J＝7.6Hz,2H),6.56(td,J＝7.6Hz,1.5Hz,2H),5.91(d,J＝7.8Hz,2H),1.38(s,12H). 13 C NMR(100MHz,CDCl 3 ):δ(ppm)145.9,139.2,134.5,134.3,125.9,122.8,122.7,139.2,134.5,88.1,24.7；
Fourth step: synthesis of rigid DOPNA receptors
1, 3-diphenoxybenzene (3 g,11.4 mmol) was dissolved in the evaporated benzene solvent under nitrogen, the reaction temperature was brought to 0 ℃ in an ice water bath, then n-butyllithium n-hexane reagent (2 m,5.5 ml) was slowly added dropwise thereto, the reaction was warmed to 70 ℃ and stirred for 4 hours; subsequently, phosphorus trichloride (1.5 mL) was added at 0deg.C, and the temperature was raised to 80deg.C and stirred for 1h; then adding settled sulfur (0.29 g) at 0 ℃, heating to 80 ℃ and stirring for 1h;subsequently, anhydrous aluminum trichloride (10.7 g) and diisopropylethylamine (4.98 mL) were added at 0deg.C, and the reaction was warmed to 80deg.C and stirred overnight. After the reaction was completed, triethylenediamine (10 g) was added, and quenched with water under an ice-water bath, the organic phase was extracted with methylene chloride, dried over anhydrous sodium sulfate, and dried by spin-drying. Finally, the product was dissolved in dichloromethane, m-chloroperoxybenzoic acid (1.3 g,7.5 mmol) was added under ice-water bath, followed by stirring at room temperature for 12h, drying over anhydrous sodium sulfate, spin-drying, dichloromethane: tetrahydrofuran (v: v) =17:1 was column chromatographed as a eluent to give the product DOPNA as a white solid in 0.85g, 30% yield. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.24-8.19(m,2H),7.65-7.59(m,3H),7.43-7.38(m,4H),6.63(dd,J＝8.4,4.4Hz,2H), 13 C NMR(400MHz,CDCl 3 ):δ(ppm)157.4,156.6,134.1,133.6,129.4,129.3,124.6,124.4,120.0,119.9,118.2,117.0,112.2,112.1,104.2,103.2. 31 PNMR(162MHz,CDCl 3 ,δ):-29.73；
Fifth step: synthesis of DOPNA-Br/DOPNA-2Br
Iron powder (0.04 g, 0.0070 mmol) and liquid bromine (0.067 mL,0.46 mmol) were added to a chloroform (15 mL) solution of DOPNA (0.1 g,0.33 mmol) under nitrogen atmosphere and stirred at 85℃for 12h. After the reaction, the sodium thiosulfate solution is quenched and extracted for 3 times with dichloromethane solution, dried over anhydrous sodium sulfate, dried by spin, and dichloromethane: ethyl acetate (v: v) =40:1 as eluent to give 0.085g of the white solid product dopa-Br in 68% yield. When the equivalent of the liquid bromine is enlarged to 4equv, 0.094g of white solid product DOPNA-2Br can be obtained, and the yield is 62%; the treatment method is the same as above;
DOPNA-Br
dichloromethane: ethyl acetate (v: v) =40:1 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.23-8.20(m,2H),7.82(d,J＝8.8Hz,1H),7.66(d,J＝6.8Hz,2H),7.45-7.42(m,3H),7.10(dd,J＝8.8,4.0Hz,1H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)157.3,157.1,155.7,152.7,137.3,133.9,133.8,129.6,129.4,129.3,125.2,120.5,120.4,120.1,120.0,113.6,105.5,104.6,104.5,104.4. 31 PNMR(162MHz,CDCl 3 ):δ(ppm)-29.95；
DOPNA-2Br
Dichloromethane: ethyl acetate (v: v) =40:1 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.24-8.19(m,2H),8.07(s,1H),7.68(t,J＝8.4Hz,2H),7.57-7.54(m,2H),7.47-7.43(m,2H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)156.9,151.8,139.6,134.1,129.3,125.4,120.4,117.4,116.6,105.0. 31 PNMR(162MHz,CDCl 3 ):δ(ppm)-29.12；
Sixth step: synthesis of the eight materials DOPNA-O, DOPNA-S, DOPNA-2O, DOPNA-2S, DOPNA-m-O, DOPNA-m-S, DOPNA-m-2O, DOPNA-m-2S
DOPNA-Br (1 equiv), SB, OB, m-SB, m-OB (1.3 equiv), pd (pph) 3 ) 4 (0.05 equiv), potassium carbonate solution (2M, 8 mL) and toluene solution (20 mL); stirring the reaction at 110 ℃ for 12 hours, extracting with dichloromethane three times after the reaction is finished, drying with anhydrous sodium sulfate, and spin-drying to obtain a crude product; DOPNA-2Br (1 equiv), SB, OB, m-SB, m-OB (2.3 equiv), pd (pph) 3 ) 4 (0.08 equiv), potassium carbonate solution (2M, 8 mL) and toluene solution (20 mL); stirring the reaction at 110 ℃ for 12 hours, extracting with dichloromethane three times after the reaction is finished, drying with anhydrous sodium sulfate, and spin-drying to obtain a crude product;
DOPNA-S
petroleum ether: ethyl acetate (v: v) =1:1; yield 67.5%. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.25-8.21(m,2H),7.81(d,J＝8.8Hz,2H),7.75(d,J＝8.8Hz,1H),7.61(dt,J＝13.6,1.6Hz,2H),7.50-7.39(m,5H),7.34-7.27(m,2H),7.07(d,J＝6.0Hz,2H),6.96-6.84(m,4H),6.43(d,J＝6.8Hz,2H). 13 C NMR(151MHz,CDCl 3 ,δ):157.5,157.2,156.0,135.5,135.3,133.8,133.6,131.7,129.7,129.3,127.0,124.9,123.0,121.6,120.2,120.0,117.1,116.6,112.7,. 31 PNMR(162MHz,CDCl 3 ):δ(ppm)-28.76；
DOPNA-O
Petroleum ether: ethyl acetate (v: v) =1:1; yield 63.2% 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.23-8.16(m,2H),7.81(d,J＝8.4Hz,2H),7.72(d,J＝8.8Hz,1H),7.60(td,J＝8.8,1.2Hz,2H),7.45-7.36(m,5H),7.31-7.28(m,2H),6.69-6.60(m,6H),6.04-6.02(m,2H). 13 C NMR(100MHz,CDCl 3 ,δ):157.5,157.2,156.1,153.1,144.0,138.4,136.4,135.3,134.3,133.8,133.6,132.1,130.8,129.6,129.3,124.7,123.3,121.5,120.2,120.0,118.5,117.7,117.3,116.7,115.5,113.4,112.8. 31 P NMR(162MHz,CDCl 3 ,δ):-28.81；
DOPNA-2S
Petroleum ether: ethyl acetate (v: v) =1:1; yield 53.8% 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.24-8.21(m,2H),7.83(dd,J＝8.8,3.6Hz,4H),7.59(t,J＝4.8Hz,3H),7.48-7.45(m,4H),7.39(d,J＝4.0Hz,2H),7.34-7.32(m,2H),7.04-7.02(m,4H),6.90-6.81(m,8H),6.39(t,J＝3.6Hz,4H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)152.4,144.1,141.1,136.5,135.3,133.8,132.2,132.1,132.0,131.8,129.7,129.7,129.5,128.6,128.5,127.0,125.0,123.0,121.6,120.1,117.1. 31 PNMR(162MHz,CDCl 3 ):δ(ppm)-28.06；
DOPNA-2O
Petroleum ether: ethyl acetate (v: v) =1:1; yield 62.1% 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.26-8.22(m,2H),7.87-7.85(m,5H),7.62(t,J＝7.2Hz,2H),7.46-7.32(m,8H),6.68-6.57(m,12H),6.03-6.00(m,4H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)157.2,157.1,157.0,152.5,152.1,152.0,144.0,138.9,138.6,138.1,136.6,136.2,135.2,134.3,134.2,134.0,133.8,132.2,132.1,131.0,129.5,125.3,123.3,121.5,115.6,113.3. 31 PNMR(162MHz,CDCl 3 ):δ(ppm)-28.16；
DOPNA-m-S
Petroleum ether: ethyl acetate (v: v) =1:1; yield 62.1% 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.19-8.13(m,2H),7.70-7.65(m,4H),7.58(t,J＝8.8Hz,1H),7.44(t,J＝7.2Hz,1H),7.41-7.30(m,4H),7.20(dd,J＝8.4,4.4Hz,1H),7.12-7.08(m,1H),7.98(d,J＝6.0Hz,2H),6.87-6.76(m,4H),6.35(d,J＝7.2Hz,2H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)157.3,157.0,156.0,153.0,144.1,141.2,138.6,135.1,133.8,133.5,131.8,130.9,129.5,129.0,126.9,126.8,124.7,122.7,120.7,120.0,116.4,112.7,112.6. 31 PNMR(162MHz,CDCl 3 ):δ(ppm)-28.88；
DOPNA-m-O
Petroleum ether: ethyl acetate (v: v) =1:1; yield 58.6% 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.22-8.16(m,2H),7.74-7.64(m,5H),7.52(t,J＝6.0Hz,1H),7.47-7.30(m,4H),7.30-7.19(m,1H),7.18-7.16(m,1H),6.70-6.65(m,6H),6.09(s,2H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)157.4,157.1,156.0,153.0,144.0,139.2,135.1,134.4,133.8,133.6,130.0,131.2,130.0,129.6,129.5,129.2,128.6,128.5,124.8,123.3,121.5,120.1,120.0,118.5,117.7,117.2,116.5,115.5,113.4,112.7. 31 PNMR(162MHz,CDCl 3 ):δ(ppm)-28.90；
DOPNA-m-2S
Petroleum ether: ethyl acetate (v: v) =1:1; YIeld 43.2% 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.18-8.13(m,2H),7.80(s,1H),7.70-7.67(m,6H),7.47(t,J＝7.2Hz,2H),7.42-7.40(m,2H),7.33(t,J＝7.6Hz,2H),7.14-7.10(m,2H),6.98(d,J＝7.0Hz,4H),6.86-6.75(m,8H),6.35(d,J＝7.2Hz,4H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)157.0,152.4,144.1,141.2,138.4,136.0,133.8,131.9,131.1,129.7,129.4,129.3,129.1,126.9,126.8,125.1,125.0,124.9,124.8,122.7,120.7,120.0,119.9,117.7,116.9,116.4. 31 PNMR(162MHz,CDCl 3 ):δ(ppm)-28.25；
DOPNA-m-2O
Petroleum ether: ethyl acetate (v: v) =1:1; yield 67.2% 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.18-8.13(m,2H),7.76(s,1H),7.70-7.67(m,4H),7.63(s,2H),7.47(t,J＝6.8Hz,2H),7.38-7.33(m,4H),7.14-7.10(m,2H),6.65-6.54(m,12H),6.03(d,J＝5.6Hz,4H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)157.0,152.4,143.9,139.2,138.9,135.9,134.4,133.8,132.1,131.3,130.2,129.5,129.4,129.3,125.1,125.0,124.9,124.8,123.3,121.5,120.0,119.9,117.7,116.9,115.5,113.4. 31 PNMR(162MHz,CDCl 3 ):δ(ppm)-28.31；
Based on the above data, eight luminescent materials synthesized in this example were DOPNA-O, DOPNA-S, DOPNA-2O, DOPNA-2S, DOPNA-m-O, DOPNA-m-S, DOPNA-m-2O, DOPNA-m-2S.
For the material DOPNA-O, DOPNA-S, DOPNA-2O, DOPNA-2S, DOPNA-m-OTest of luminescence properties of DOPNA-m-S, DOPNA-m-2O, DOPNA-m-2S: the eight luminescent materials are respectively dissolved in toluene to prepare the light-emitting material with the concentration of 1.0X10 -4 The luminescence spectrum of the mol/L solution under the excitation of ultraviolet light of 360nm and 380nm is shown in figure 2. The CIE 1931 chromaticity coordinates of the spectra were (0.152,0.130), (0.158,0.183), (0.172,0.220), (0.161,0.176), (0.154,0.134), (0.164,0.198), (0.160,0.170), (0.165,0.198) indicating that they are deep blue, blue light emitting materials. The luminous efficiencies of these solutions were measured using an integrating sphere, and the luminous quantum efficiencies reached 0.55, 0.45, 0.58, 0.37, 0.75, 0.32, 0.61, and 0.20. The life of the material DOPNA-O, DOPNA-2O, DOPNA-m-O, DOPNA-m-2O was tested, and the material was dissolved in degassed toluene and configured to have a concentration of 1.0X10 -4 The detection wavelength of the mol/L solution is 450nm. The specific attenuation curve is shown in fig. 3. These four materials have a significant thermal retardation effect as can be seen from their decay curves. Their instantaneous and delayed lifetimes were 3.39 ns/3.28 μs, 4.84 ns/2.92 μs, 11.0 ns/6.9 μs, 2.18 ns/5.0 μs, respectively.
Example two
The structural formula of the luminescent material DOPNA-p-O (para substitution) synthesized by the embodiment is as follows:
Figure BDA0002285295410000181
the specific synthetic route is shown in figure 1; the specific synthesis steps are as follows:
the first step: triiodo-1, 3-diphenoxybenzene synthesis
2.6-difluoro-p-bromoiodobenzene (0.32 g,1.01 mmol), o-iodophenol (0.88 g,4.00 mmol) and potassium carbonate (0.552 mg,4.00 mmol) were added to the reaction tube under nitrogen atmosphere, followed by 15mL of NMP (N-methylpyrrolidone) and reacted at 135℃for 12 hours; filtering after the reaction is completed, washing with petroleum ether for three times, and combining organic solutions and concentrating; purifying the crude product by a silica gel column, wherein the eluent is petroleum ether, and the final product is white solid 0.31g, and the yield is 43%; 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.92(dd,J＝8.4,1.6Hz,2H),7.39-7.35(m,2H),7.00-6.96(m,4H),6.54(s,2H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)158.5,155.2,140.3,130.0,126.6,123.0,120.2,115.3,89.0,81.0；
and a second step of: synthesis of DOPNA-p-Br
Triiodo-1, 3-diphenoxybenzene (0.48 g,0.67 mmol) was dissolved in the evaporated meta-xylene solution under nitrogen atmosphere, n-butyllithium/n-hexane reagent (0.8 mL,2.0 mmol) was slowly added dropwise at-78deg.C, and stirred for 1h; after the reaction was returned to-30 ℃, a phosphorus trichloride solution (0.057 mL,0.65 mmol) was slowly added dropwise, and the mixture was stirred for 2 hours, and after the reaction was returned to room temperature, the mixture was stirred for 12 hours. Then 4mL of hydrogen peroxide is slowly added and stirred for 1h. Extracting with dichloromethane three times, mixing organic phases, drying with anhydrous sodium sulfate, concentrating, purifying with silica gel column, eluting with dichloromethane: ethyl acetate (v: v) =10:1. The final product was a white solid, 0.03g, 12% yield; 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.23-8.17(m,2H),7.64(t,J＝8.4Hz,2H),7.44-7.40(m,4H),7.36(d,J＝4.4Hz,2H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)156.8,129.6,124.4,120.8,120.4,120.1,120.0,119.4,115.8. 31 PNMR(162MHz,CDCl 3 ):δ(ppm)-29.98；
and a third step of: synthesis of DOPNA-p-O
DOPNA-p-Br (0.06 g,0.156 mmol), OB (0.078 g,0.20 mmol), pd (pph) 3 ) 4 (0.01 g,0.009 mmol), potassium carbonate solution (2M, 5 mL) and toluene solution (15 mL); stirring the reaction at 110 ℃ for 12 hours, extracting with dichloromethane three times after the reaction is finished, drying with anhydrous sodium sulfate, and spin-drying to obtain a crude product. The eluent is petroleum ether: ethyl acetate (v: v) =1:5; the final product was a white solid, 0.034g, 40% yield; 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.27-8.22(m,2H),7.88(d,J＝8.4Hz,2H),7.66(t,J＝8.0Hz,2H),7.52-7.41(m,8H),6.73-6.61(m,6H),6.01(d,J＝7.6Hz,2H). 13 C NMR(400MHz,CDCl 3 ):δ(ppm)157.5,157.1,146.5,144.0,139.7,139.4,134.2,133.7,131.6,130.0,129.5,124.8,123.3,121.6,120.1,118.1,117.3,115.6,113.3,110.9. 31 P NMR(162MHz,CDCl 3 ):δ(ppm)-29.65；
test of luminescence properties of the material DOPNA-p-O: the luminescent material DOPNA-p-O was dissolved in toluene to give a concentration of 1.0X10 -4 The luminescence spectrum of the mol/L solution is shown in figure 2 under the excitation of 380nm ultraviolet light; the CIE 1931 chromaticity coordinate of the spectrum is (0.243,0.462), which shows that the spectrum has high green color purity; the luminous efficiency of the solution is measured by adopting an integrating sphere, and the luminous quantum efficiency reaches 0.75. The life of the material DOPNA-p-O was tested and the material was dissolved in degassed toluene and configured to a concentration of 1.0X10 -4 The detection wavelength of the solution in mol/L is 520nm; specific decay curves as can be seen in fig. 3, this material has a significant thermal delay effect from their decay curves; their instantaneous lifetime and delay lifetime are 4.53 ns/4.45 μs, respectively.
The above description of the embodiments of the invention has been presented in connection with the drawings but these descriptions should not be construed as limiting the scope of the invention, which is defined by the appended claims, and any changes based on the claims are intended to be covered by the invention.

Claims (5)

1. A thermally activated delayed fluorescence material based on the conformational locking of triphenylphosphine oxide receptors, characterized in that it has a structure represented by the formula:
Figure FDA0004143263090000011
R 1 a structure selected from one of:
Figure FDA0004143263090000012
2. the thermally activated delayed fluorescence material based on the ether linkage conformational lock triphenylphosphine oxide acceptor according to claim 1, which has a structure represented by the formula:
Figure FDA0004143263090000013
3. the thermally activated delayed fluorescence material based on the ether linkage conformational lock triphenylphosphine oxide acceptor according to claim 1, which has a structure represented by the formula:
Figure FDA0004143263090000021
4. the thermally activated delayed fluorescence material based on the ether linkage conformational lock triphenylphosphine oxide acceptor according to claim 1, which has a structure represented by the formula:
Figure FDA0004143263090000022
/>
5. the thermally activated delayed fluorescence material based on the ether linkage conformational lock triphenylphosphine oxide acceptor according to claim 1, which has a structure represented by the formula:
Figure FDA0004143263090000023
/>
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