D-A-D racemic 3D chiral fluorescent compound as well as preparation method, resolution method and application thereof
By developing D-A-D type racemic 3D chiral fluorescent compound, using the spatial electron transfer characteristics and bridge structure, the existing chiral circular polarization luminescent molecules have been solved, and efficient luminescent performance and chiral circular polarization luminescent activity have been achieved.
Patent Information
- Application Number
- CN202510092684.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-21
- Publication Date
- 2025-05-02
AI Technical Summary
The existing chiral circularly polarized luminescent molecules are limited in types, and the presence of heavy atoms leads to low luminescence efficiency, limiting the application of materials.
A D-A-D type racemic 3D chiral fluorescent compound was developed to improve luminescence performance through the electron transfer characteristics and bridge structure of the space, and resolved into enantiomers through high-performance liquid chromatography.
It achieves efficient luminescence performance and chiral circular polarization luminescence activity, overcomes the problem of limited types of chiral circular polarization luminescence molecules, and improves luminescence efficiency.
Smart Images
Figure CN119912406A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of organic light-emitting materials, and in particular to a DAD-type racemic 3D chiral fluorescent compound and a preparation method, a separation method and an application thereof. Background Art
[0002] Circularly polarized luminescence (CPL) refers to the phenomenon that a chiral luminescent system emits differential left-handed and right-handed circularly polarized light after being stimulated. The circularly polarized luminescent materials developed from this have broad application prospects in asymmetric catalysis, chemical sensors / probes, liquid crystal display backlight sources, 3D displays, optical anti-counterfeiting and other fields. Traditional CPL materials are mainly chiral lanthanide complexes. However, the presence of heavy atoms leads to generally low luminescence efficiency of molecular systems, which greatly limits the application of such materials. Circularly polarized luminescent chiral organic small molecules have the advantages of simple molecular structure, high luminescence efficiency, a wide variety, and easy derivatization. They have become a research hotspot in the field of CPL materials. However, the types of existing chiral circularly polarized luminescent molecules are limited. Summary of the invention
[0003] In view of this, the present application provides a DAD-type racemic 3D chiral fluorescent compound and a preparation method, a separation method and an application thereof. The 3D chiral fluorescent compound has a bridged structure. The key is that the compound has good luminescence performance through the spatial electron transfer characteristics. At the same time, due to the steric hindrance, the compound has a 3D stereo configuration, and also has chirality and exhibits circularly polarized luminescence activity, which can effectively overcome the defects of the limited types of existing chiral circularly polarized luminescent molecules.
[0004] In a first aspect, the present application provides a DAD-type racemic 3D chiral fluorescent compound, wherein the racemic 3D chiral fluorescent compound has a general structural formula as shown in Rac-formula TM:
[0005]
[0006] Among them, the electron donor is an electron donor unit with electron donating properties, which is triphenylamine or its derivatives; the electron acceptor is an electron acceptor unit with electron withdrawing properties, which is selected from one of benzothiadiazole, benzoselenadiazole, pyrazine or its derivatives, dicyanobenzene or its derivatives, benzophenone, fluorenone, diphenyl sulfone or its derivatives, and triazine; the bridge is a bridge structure, and the bridge structure is naphthalene or its derivatives / anthracene or its derivatives.
[0007] Preferably, the electron donor is selected from one of the following structural formulas:
[0008] and / or
[0009] The electron acceptor is selected from one of the following structural formulas:
[0010]
[0011] And / or the bridging structure is selected from one of the following structural formulas:
[0012]
[0013] Preferably, the 3D chiral fluorescent compound is selected from one of the following structural formulas:
[0014]
[0015] The second aspect of the present application also provides a method for preparing the above-mentioned DAD-type racemic 3D chiral fluorescent compound, comprising the following synthesis steps:
[0016] S1, the compound represented by Formula 1 and the compound represented by Formula 2 are subjected to Suzuki coupling reaction under palladium catalyst and alkaline conditions to obtain a compound represented by Formula 3;
[0017]
[0018] S2, the compound represented by formula 3 and bis(pinacol)diboron are subjected to Suzuki-miyaura reaction in the presence of a palladium catalyst and alkaline conditions to obtain a compound represented by formula 4;
[0019]
[0020] S3, the compound represented by Formula 4 and the compound represented by Formula 5 are subjected to Suzuki coupling reaction in the presence of a palladium catalyst and alkaline conditions to obtain a racemic Rac-compound represented by Formula TM;
[0021]
[0022] Specifically, the compound of formula 1 may be of the following structure:
[0023]
[0024] Specifically, the compound of formula 2 may be of the following structure:
[0025]
[0026] Specifically, the compound of formula 3 may be of the following structure:
[0027] Specifically, the compound of formula 4 may be of the following structure:
[0028]
[0029] Specifically, the compound of formula 5 may be of the following structure:
[0030]
[0031] Preferably, in step S1, the specific process of the Suzuki coupling reaction is: the compound represented by Formula 1 and the compound represented by Formula 2 are dissolved in a solvent, and a palladium catalyst and a base are added, and the reaction is carried out under an inert gas atmosphere, and the reaction temperature is 60-160° C., specifically 75° C., and the reaction time is 6-48 hours, specifically 16 hours;
[0032] Specifically, after the reaction, the system is cooled to room temperature, the solvent is removed by a rotary evaporator, and then the organic phase is extracted with dichloromethane and washed with saturated brine. The extracted organic phase is dried with anhydrous sodium sulfate, filtered, and then the solvent is removed by a rotary evaporator to obtain a crude product; finally, the crude product is purified by column chromatography, and the eluent is a mixed solvent of petroleum ether and dichloromethane;
[0033] The solvent is selected from tetrahydrofuran, acetonitrile, toluene, xylene, ethylene glycol diethyl ether, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, and can be specifically tetrahydrofuran; the palladium catalyst is tetrakis(triphenylphosphine)palladium or [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium, and can be specifically tetrakis(triphenylphosphine)palladium; the base is selected from cesium carbonate, potassium carbonate, sodium carbonate, lithium carbonate, potassium phosphate, cesium fluoride, potassium hydroxide, and sodium hydroxide, and can be specifically an aqueous solution of sodium carbonate; the molar ratio of the compound of formula 2 to the compound of formula 1 is 1:(1-3), and can be specifically 1:2; the molar ratio of the compound of formula 1 to the palladium catalyst is 1:(0.01-0.1), and can be specifically 1:0.01; the molar ratio of the compound of formula 1 to the base is 1:(3-100), and can be specifically 1:50.
[0034] Preferably, in step S2, the specific process of the Suzuki-miyaura reaction is: the compound represented by formula 3 and bis(pinacol)diboron are dissolved in a solvent, and a palladium catalyst and a base are added, and the reaction is carried out under an inert gas atmosphere, and the reaction temperature is 80-120° C., specifically 80° C., and the reaction time is 8-24 hours, specifically 16 hours;
[0035] Specifically, after the reaction, the system is cooled to room temperature, the solvent is removed by a rotary evaporator, and then the organic phase is extracted with dichloromethane and washed with saturated brine. The extracted organic phase is dried with anhydrous sodium sulfate, filtered, and then the solvent is removed by a rotary evaporator to obtain a crude product; finally, the crude product is purified by column chromatography, and the eluent is a mixed solvent of petroleum ether and dichloromethane;
[0036] The solvent is selected from one of ethylene glycol diethyl ether, toluene, xylene, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, and can be specifically dioxane; the palladium catalyst is [1,1-bis(diphenylphosphino)ferrocene]palladium dichloride; the base is potassium acetate or sodium acetate, and can be specifically potassium acetate; the molar ratio of the compound of formula 3 to bis(pinacol)diboron is 1:(1-3), and can be specifically 1:1.5; the molar ratio of the compound of formula 3 to the palladium catalyst is 1:(0.01-0.1), and can be specifically 1:0.01; the molar ratio of the compound of formula 3 to the base is 1:(3-10), and can be specifically 1:4.
[0037] Preferably, in step S3, the specific process of the Suzuki coupling reaction is: the compound represented by Formula 4 and the compound represented by Formula 5 are dissolved in a solvent, and a palladium catalyst and a base are added, and the reaction is carried out under an inert gas atmosphere, and the reaction temperature is 60-160° C., specifically 105° C., and the reaction time is 6-48 hours, specifically 12 hours;
[0038] Specifically, after the reaction, the system is cooled to room temperature, the solvent is removed by a rotary evaporator, and then the organic phase is extracted with dichloromethane and washed with saturated brine. The extracted organic phase is dried with anhydrous sodium sulfate, filtered, and then the solvent is removed by a rotary evaporator to obtain a crude product; the crude product is purified by column chromatography, and the eluent is a mixed solvent of petroleum ether and dichloromethane;
[0039] The solvent is selected from tetrahydrofuran, acetonitrile, toluene, xylene, ethylene glycol diethyl ether, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, and can be specifically tetrahydrofuran or dioxane; the palladium catalyst is tetrakis(triphenylphosphine)palladium or [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium, and can be specifically tetrakis(triphenylphosphine)palladium; the base is selected from cesium carbonate, potassium carbonate, sodium carbonate, One of lithium, potassium phosphate, cesium fluoride, potassium hydroxide, and sodium hydroxide, specifically an aqueous solution of potassium carbonate or sodium carbonate; the molar ratio of the compound of formula 5 to the compound of formula 4 is 1:(2.2-4), specifically 1:2.2; the molar ratio of the compound of formula 5 to the palladium catalyst is 1:(0.01-0.1), specifically 1:0.02; the molar ratio of the compound of formula 5 to the base is 1:(3-100), specifically 1:50.
[0040] The third aspect of the present application also provides a method for resolving the above-mentioned DAD-type racemic 3D chiral fluorescent compound, comprising the following synthesis steps:
[0041] The DAD-type racemic 3D chiral fluorescent compound Rac-formula TM was separated into formula TMpeak1 and formula TMpeak2 by chiral high performance liquid chromatography to obtain enantiomers;
[0042]
[0043] Preferably, the high performance liquid chromatography uses a chiral column for separation, and the chiral column used is purchased from Daicel Pharmaceutical Chiral Technology (Shanghai) Co., Ltd., and its model is selected from one of IA, IB, IB N-5, IC, ID, IE, IF, IG, IH, IJ, IK, and IM; the mobile phase of the high performance liquid chromatography is selected from one of chromatographic n-hexane, chromatographic dichloromethane, chromatographic tetrahydrofuran, chromatographic ethyl acetate, chromatographic methanol, and chromatographic isopropanol, and a mixture of two or more of them in any proportion.
[0044] The fourth aspect of the present application also provides the use of the above-mentioned DAD-type racemic 3D chiral fluorescent compound in the preparation of organic electroluminescent devices and circularly polarized luminescence.
[0045] Compared with the prior art, this application has the following beneficial effects:
[0046] 1. The donor, acceptor and bridging structure used in this application are simple and easy to obtain. They can be directly purchased commercially or prepared through simple organic synthesis. The raw materials are cheap and easy to obtain, and the yield of the final product is high, which is conducive to expanding scale production. This application can provide a new strategy for the field of chiral optoelectronic materials.
[0047] 2. The Rac-formula TM provided in the present application is a fluorescent molecule with spatial charge transfer; the Rac-formula TM is a racemic organic compound containing a pair of enantiomers, which can be separated into single enantiomers by high performance liquid chromatography; in addition, the synthesis method of the Rac-formula TM provided in the present application is simple, the synthesis steps are simple and efficient, and the product is easy to separate and purify. BRIEF DESCRIPTION OF THE DRAWINGS
[0048] In order to more clearly illustrate the technical solutions in the present application or the prior art, the drawings required for use in the description of the present application or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.
[0049] Figure 1 It is the UV and fluorescence spectrum of Rac-formula TM-3 in dilute toluene solution;
[0050] Figure 2 (a) is the chiral liquid phase analysis of the racemate of Formula TM6, and the chiral liquid phase analysis of the first (b) and second (c) optically pure components obtained after resolution of the racemate of Formula TM6;
[0051] Figure 3 Circular dichroism spectra and circularly polarized luminescence diagrams of optically pure components of (a) TM3 and (b) TM6. DETAILED DESCRIPTION
[0052] In order to make the purpose, technical solutions and advantages of this application clearer, the technical solutions in this application will be clearly and completely described below in conjunction with the drawings in this application. Obviously, the described embodiments are part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.
[0053] Unless otherwise specified, the experimental methods used in the examples of this application are all conventional methods.
[0054] In the following examples, unless otherwise specified, all raw materials can be obtained by commercial purchase or conventional methods.
[0055] Example 1
[0056] Formula 5-3 in the following examples is based on the paper reported by Duan Lian et al. in 2021 entitled: Approaching Nearly 40% External Quantum Efficiency in Organic Light Emitting Diodes Utilizing a Green Thermally Activated Delayed Fluorescence Emitter with an Extended Linear Donor-Acceptor-Donor Structure. (Advanced Materials, 33 (44), 2103293.) The raw materials required for the synthesis can be obtained from commercial sources. The synthesis route is as follows:
[0057]
[0058] The compound of formula 3 is implemented by selecting the following structure:
[0059]
[0060] The specific steps are as follows (taking formula 3-1 as an example):
[0061]
[0062] Synthesis of Formula 3-1: Take 1,8-dibromonaphthalene (4.29g, 15mmol), triphenylamine-4-boric acid (2.17g, 7.5mmol), tetrakistriphenylphosphine palladium (87mg, 0.075mmol) and dissolve them in 60ml tetrahydrofuran, then add sodium carbonate aqueous solution (2M, 30ml), stir and reflux the reaction solution at 75°C in a nitrogen atmosphere for 16h, and then remove the solvent by vacuum distillation on a rotary evaporator, extract the residue with 30ml×3 dichloromethane and wash the extract with saturated sodium chloride solution, dry the extract with sodium sulfate, concentrate it on a rotary evaporator and purify it by column chromatography to obtain a light yellow solid (yield 58%). HRMS (ESI): m / z[M+H] + Calculate for C 28 H 21 Bn + :452.0832;found:452.0821.
[0063] Synthesis of Formula 3-2: Refer to the synthesis of Formula 3-1 to obtain a white solid (yield 60%). HRMS (APCI): m / z [M+H] + Calculate for C 28 H 19 Bn +:448.0696;found:448.0652.
[0064] Synthesis of Formula 3-3: Referring to the synthesis of Formula 3-1, a light yellow solid was obtained (yield 56%).
[0065] Synthesis of Formula 3-4: Referring to the synthesis of Formula 3-1, a white solid was obtained (yield 57%).
[0066] Synthesis of Formula 3-5: Refer to the synthesis of Formula 3-1 to obtain a yellow solid (yield 50%). HRMS (ESI): m / z [M+H] + Calculate for C 30 H 25 BrNO2 + :510.1064;found:510.1039.
[0067] Synthesis of Formula 3-6: Referring to the synthesis of Formula 3-1, a light yellow solid was obtained (yield 53%). HRMS (ESI): m / z [M+H] + Calculate for C 28 H 19 BrNO + :464.0645; found:464.0586. The specific reactants, products and yields are shown in Table 1.
[0068] Table 1
[0069]
[0070]
[0071] The compound of formula 4 is implemented by selecting the following structure:
[0072]
[0073] The specific steps are as follows (taking formula 4-1 as an example):
[0074]
[0075] Synthesis of Formula 4-1: Take the intermediate Formula 3-1 (2.25g, 5mmol), pinacol diboron (1.9g, 7.5mmol), [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride (73mg, 0.1mmol), potassium acetate (1.84g, 18.75mmol) and dissolve them in 40ml of dry 1,4-dioxane, stir and react at 85℃ in a nitrogen atmosphere for 16h, and then remove the solvent by vacuum distillation on a rotary evaporator, extract the residue with 30ml×3 dichloromethane and wash the extract with a saturated sodium chloride solution, dry the extract with sodium sulfate, concentrate it on a rotary evaporator and purify it by column chromatography to obtain a white solid (yield 85%). HRMS (ESI): m / z[M+H] + Calculate for C 34 H 33 BNO2 + :498.2599;found:498.2587.
[0076] Synthesis of Formula 4-2: Refer to the synthesis of Formula 4-1 to obtain a white solid (yield 89%). HRMS (ESI): m / z [M+H] + Calculate for C 34 H 31 BNO2 + :496.2443;found:496.2444.
[0077] Synthesis of Formula 4-3: Referring to the synthesis of Formula 4-1, a white solid was obtained (yield 82%).
[0078] Synthesis of Formula 4-4: Referring to the synthesis of Formula 4-1, a white solid was obtained (yield 87%).
[0079] Synthesis of Formula 4-5: Refer to the synthesis of Formula 4-1 to obtain a white solid (yield 82%). HRMS (ESI): m / z [M+H] + Calculate for C 36 H 37 BNO4 + :558.2811;found:558.2743.
[0080] Synthesis of Formula 4-6: Referring to the synthesis of Formula 4-1, a light yellow solid was obtained (yield 83%). HRMS (ESI): m / z [M+H] + Calculate for C 34 H 31 BNO3 + :512.2392; found:512.2373. The specific reactants, products and yields are shown in Table 2.
[0081] Table 2
[0082]
[0083]
[0084] The formula Rac-TM compound selects the following structure for implementation:
[0085]
[0086] The specific steps are as follows (taking Rac-formula TM-1 as an example):
[0087]
[0088] Synthesis of Rac-formula TM-1: Take 4,7-dibromo-2,1,3-benzothiadiazole (0.294g, 1mmol), compound formula 4-1 (1.1g, 2.2mmol), tetrakistriphenylphosphine palladium (23mg, 0.02mmol) and dissolve them in 50ml of tetrahydrofuran, then add sodium carbonate aqueous solution (2M, 30ml), and the reaction solution is stirred and refluxed at 75°C in a nitrogen atmosphere for 24h. After the reaction, the solvent is removed by reduced pressure distillation on a rotary evaporator, the residue is extracted with dichloromethane 30ml×3 and the extract is washed with saturated sodium chloride solution. The extract is dried over sodium sulfate, concentrated by a rotary evaporator and purified by column chromatography to obtain a yellow solid (yield 85%). 1 H NMR(400MHz,Chloroform-d)δ7.95(dd,J=8.2,1.4Hz,4H),7.62–7.53(m,4H),7.4 6(dd,J=8.2,7.0Hz,2H),7.29(dd,J=7.0,1.4Hz,2H),7.26(s,2H),7.02(t,J=7.7H z,8H),6.90(t,J=7.3Hz,4H),6.85–6.74(m,8H),6.70(dd,J=8.4,2.2Hz,2H),6.5 4(dd,J=8.4,2.5Hz,2H), 6.40(dd,J=8.4,2.2Hz,2H), 6.05(dd,J=8.4,2.5Hz,2H).
[0089] Example 2
[0090] Synthesis of Rac-Formula TM-2: Referring to the synthesis of Rac-Formula TM-1, a yellow-green solid was obtained (yield 89%). 1HNMR(400MHz,Chloroform-d)δ8.12(dd,J=7.7,1.0Hz,4H),7.94(dd,J=8.3,1.4Hz,2H),7.67(dd,J=8.3,1.4Hz,2H),7.56(dd,J=8.1,7.0Hz,2H),7. 33–7.28(m,4H),7.21(ddd,J=7.9,4.7,3.3Hz,4H),7.15–6.94(m,12H),6. 81–6.75(m,4H),6.68(dd,J=8.1,2.3Hz,2H),6.45(dd,J=8.2,7.0Hz,2H).
[0091] Example 3
[0092] Synthesis of Rac-formula TM-3: Referring to the synthesis of Rac-formula TM-1, a light yellow solid was obtained (yield 90%). 1 HNMR(400MHz,Chloroform-d)δ8.46(s,2H),7.97(ddd,J=8.2,5.0,1.4Hz,4H),7.60(dd, J=7.0,1.5Hz,2H),7.52(ddd,J=12.2,8.2,7.0Hz,4H),7.46(s,2H),7.23(dd,J=7.0,1.4H z,2H),7.14–7.06(m,8H),6.99–6.92(m,4H),6.91–6.83(m,8H),6.64(dd,J=8.4,2.2Hz,2 H), 6.55 (dd, J=8.4, 2.5Hz, 2H), 6.30 (dd, J=8.4, 2.2Hz, 2H), 5.98 (dd, J=8.4, 2.5Hz, 2H).
[0093] Example 4
[0094] Synthesis of Rac-Formula TM-4: Referring to the synthesis of Rac-Formula TM-1, a light yellow solid was obtained (yield 89%). 1 HNMR(400MHz,Chloroform-d)δ8.52(s,2H),7.96(dd,J=8.1,1.5Hz,4H),7.60(dd,J=7.0,1.4Hz,2H),7.56–7.47(m,4H) ,7.39(s,2H),7.25(d,J=7.0Hz,2H),7.09(d,J=8.0Hz,8H),6.92–6.48(m,12H),6.28(s,2H),5.99(s,2H),1.28(s,36H).
[0095] Example 5
[0096] Synthesis of Rac-formula TM-5: Referring to the synthesis of Rac-formula TM-1, a light yellow solid was obtained (yield 92%). 1 HNMR(400MHz,Chloroform-d)δ8.71(s,2H),8.13(dt,J=7.8,1.0Hz,4H),7.93(dd,J=8.2,1.3Hz,2H),7.68(dd,J=8.3,1.4Hz,2H),7.52(dd,J=8 .1,7.0Hz,2H),7.37(s,2H),7.25–7.19(m,6H),7.18–7.00(m,12H),6.7 8(dd,J=7.1,1.4Hz,2H), 6.68–6.59(m,4H), 6.43(dd,J=8.2,7.0Hz,2H).
[0097] Example 6
[0098] Synthesis of Rac-formula TM-6: Referring to the synthesis of Rac-formula TM-1, a white solid was obtained (yield 90%). 1 H NMR(400MHz,Chloroform-d)δ8.73(s,2H),8.12(d,J=1.9Hz,4H),7.90(dd,J=8.2 ,1.4Hz,2H),7.64(dd,J=8.3,1.4Hz,2H),7.51(dd,J=8.2,6.9Hz,2H),7.38(s,2H ),7.24(dd,J=6.9,1.3Hz,2H),7.19–7.11(m,6H),7.05–6.96(m,6H),6.76(dd,J= 7.0, 1.4Hz, 2H), 6.59 (d, J = 1.3Hz, 4H), 6.35 (dd, J = 8.2, 7.0Hz, 2H), 1.47 (s, 36H).
[0099] Example 7
[0100] Synthesis of Rac-formula TM-7: Referring to the synthesis of Rac-formula TM-1, a light yellow solid was obtained (yield 88%). 1 H NMR (400MHz, Chloroform-d) δ8.53 (s, 2H), 7.96 (dd, J=8.3, 1.3Hz, 2H), 7.85 (dd, J=7. 9,1.7Hz,2H),7.58–7.49(m,4H),7.25–7.16(m,6H),7.14–5.73(m,20H),5.30(s,4H).
[0101] Example 8
[0102] Synthesis of Rac-formula TM-8: Referring to the synthesis of Rac-formula TM-1, a light yellow solid was obtained (yield 87%). 1 H NMR(400MHz,Chloroform-d)δ9.04(d,J=1.8Hz,2H),8.86(s,2H),8.41(d,J=8.4Hz,2H),8.09–8.01(m,4H),7.70–7.62(m,8H),7.53(d d,J=7.1,1.3Hz,2H),7.03–6.95(m,4H),6.82–6.77(m,12H),6.60(d,J=8.2Hz,2H),6.43(dd,J=6.9,2.9Hz,8H),6.20(d,J=7.9Hz,2H).
[0103] Example 9
[0104] Synthesis of Rac-formula TM-9: Referring to the synthesis of Rac-formula TM-1, a light yellow solid was obtained (yield 86%). 1 H NMR(400MHz,Chloroform-d)δ9.03(d,J=1.9Hz,2H),8.79(s,2H),8.26(d,J=8.5Hz,2H),7.92(dq,J=8.1,4.6,4.0Hz,4H),7.54(t,J=7.6Hz,2 H),7.51–7.46(m,6H),7.42(d,J=7.0Hz,2H),6.89(d,J=8.3Hz,2H),6. 83–6.67(m,10H),6.49(s,2H),6.24(s,8H),6.00(s,2H),1.07(s,36H).
[0105] Example 10
[0106] Synthesis of Rac-formula TM-10: Referring to the synthesis of Rac-formula TM-1, a white solid was obtained (yield 88%).
[0107] Embodiment 11
[0108] Synthesis of Rac-Formula TM-11: Referring to the synthesis of Rac-Formula TM-1, a white solid was obtained (yield 90%).
[0109] The specific reactants, products and yields of each example are shown in Table 3.
[0110] Table 3
[0111]
[0112]
[0113]
[0114] Characterization and performance testing
[0115] 1. UV and fluorescence spectra of Rac-formula TM in dilute toluene solution (taking Rac-formula TM-3 as an example, the results are as follows Figure 1 The data results of each embodiment are shown in Table 4.
[0116] Table 4
[0117]
[0118]
[0119] 2. HPLC separation of Rac-formula TM enantiomers (taking Rac-formula TM-6 as an example, the results are as follows Figure 2 The data results of each embodiment are shown in Table 5.
[0120] Table 5
[0121] Compound Peak1 retention time (min) Peak2 retention time (min) Rac-style TM-1 3.145 3.987 Rac-style TM-2 2.840 3.638 Rac-style TM-3 3.247 3.458 Rac-style TM-4 2.830 3.323 Rac-style TM-5 2.929 3.345 Rac-style TM-6 2.821 3.836 Rac-style TM-7 4.450 6.363 Rac-style TM-8 4.309 5.193 Rac-style TM-9 3.037 4.793 Rac-style TM-10 4.135 5.102 Rac-style TM-11 4.076 5.011
[0122] 3. In a dilute toluene solution, the ultraviolet absorption peaks of the DAD-type racemic 3D chiral fluorescent compounds determined above are all around 300nm, and exhibit significant photoluminescence performance. In addition, these racemates were analyzed by chiral high performance liquid chromatography, and two equal isomeric components with different retention times were observed. A 50mg / ml exosome solution was prepared using chromatographic dichloromethane, and the enantiomers were separated by semi-preparative or preparative chiral liquid chromatography, with an injection volume of 100 to 1000 microliters. The two components were collected according to the peak time and evaporated and concentrated by a rotary evaporator to obtain a solid, and its optical purity was verified by analytical chiral liquid chromatography. A dilute solution of an optically pure enantiomer was prepared and its circular dichroism and circular polarization luminescence properties were measured, all of which showed significant chiral optical activity, indicating that this type of 3D chiral fluorescent compound has application potential as a chiral optical material. Circular dichroism and circular polarized luminescence of Rac-TM enantiomers in dichloromethane (taking TM-3 and TM-6 as examples, the results are shown in Figure 3 shown).
[0123] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.
Claims
1. A DAD type racemic 3D chiral fluorescent compound, characterized in that: The general structural formula of the racemic 3D chiral fluorescent compound is shown in Rac-Formula TM: Among them, the electron donor is an electron donor unit with electron donating properties, which is triphenylamine or its derivatives; the electron acceptor is an electron acceptor unit with electron withdrawing properties, which is selected from one of benzothiadiazole, benzoselenadiazole, pyrazine or its derivatives, dicyanobenzene or its derivatives, benzophenone, fluorenone, diphenyl sulfone or its derivatives, and triazine; the bridge is a bridge structure, and the bridge structure is naphthalene or its derivatives / anthracene or its derivatives.
2. The DAD type racemic 3D chiral fluorescent compound according to claim 1, characterized in that: The electron donor is selected from one of the following structural formulas: and / or The electron acceptor is selected from one of the following structural formulas: and / or The bridging structure is selected from one of the following structural formulas:
3. The DAD type racemic 3D chiral fluorescent compound according to claim 1, characterized in that: The 3D chiral fluorescent compound is selected from one of the following structural formulas:
4. A method for preparing a DAD-type racemic 3D chiral fluorescent compound according to any one of claims 1 to 3, characterized in that: The synthesis steps include: S1, the compound represented by Formula 1 and the compound represented by Formula 2 are subjected to Suzuki coupling reaction under palladium catalyst and alkaline conditions to obtain a compound represented by Formula 3; S2, the compound represented by formula 3 and bis(pinacol)diboron are subjected to Suzuki-miyaura reaction in the presence of a palladium catalyst and alkaline conditions to obtain a compound represented by formula 4; S3, the compound represented by Formula 4 and the compound represented by Formula 5 are subjected to Suzuki coupling reaction in the presence of a palladium catalyst and alkaline conditions to obtain a racemic Rac-compound represented by Formula TM; 5. The method for preparing a DAD type racemic 3D chiral fluorescent compound according to claim 4, characterized in that: In step S1, the specific process of the Suzuki coupling reaction is: the compound represented by formula 1 and the compound represented by formula 2 are dissolved in a solvent, and a palladium catalyst and a base are added, and the reaction is carried out under an inert gas atmosphere, and the reaction temperature is 60-160° C. and the reaction time is 6-48 hours; Wherein, the solvent is selected from one of tetrahydrofuran, acetonitrile, toluene, xylene, ethylene glycol diethyl ether, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; the palladium catalyst is tetrakis(triphenylphosphine)palladium or [1,1-bis(diphenylphosphino)ferrocene]palladium dichloride; the base is selected from one of cesium carbonate, potassium carbonate, sodium carbonate, lithium carbonate, potassium phosphate, cesium fluoride, potassium hydroxide, and sodium hydroxide; the molar ratio of the compound of formula 2 to the compound of formula 1 is 1:(1-3); the molar ratio of the compound of formula 1 to the palladium catalyst is 1:(0.01-0.1); and the molar ratio of the compound of formula 1 to the base is 1:(3-100).
6. The method for preparing a DAD type racemic 3D chiral fluorescent compound according to claim 4, characterized in that: In step S2, the specific process of the Suzuki-miyaura reaction is as follows: the compound represented by formula 3 and bis(pinacol)diboron are dissolved in a solvent, and a palladium catalyst and a base are added to react under an inert gas atmosphere, and the reaction temperature is 80-120° C. and the reaction time is 8-24 hours; Wherein, the solvent is selected from one of ethylene glycol diethyl ether, toluene, xylene, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; the palladium catalyst is [1,1-bis(diphenylphosphino)ferrocene]palladium dichloride; the base is potassium acetate or sodium acetate; the molar ratio of the compound of formula 3 to bis(pinacol)diboron is 1:(1-3); the molar ratio of the compound of formula 3 to the palladium catalyst is 1:(0.01-0.1); and the molar ratio of the compound of formula 3 to the base is 1:(3-10).
7. The method for preparing a DAD type racemic 3D chiral fluorescent compound according to claim 4, characterized in that: In step S3, the specific process of the Suzuki coupling reaction is: the compound represented by formula 4 and the compound represented by formula 5 are dissolved in a solvent, and a palladium catalyst and a base are added, and the reaction is carried out under an inert gas atmosphere, and the reaction temperature is 60-160° C. and the reaction time is 6-48 hours; Wherein, the solvent is selected from one of tetrahydrofuran, acetonitrile, toluene, xylene, ethylene glycol diethyl ether, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; the palladium catalyst is tetrakis(triphenylphosphine)palladium or [1,1-bis(diphenylphosphino)ferrocene]palladium dichloride; the base is selected from one of cesium carbonate, potassium carbonate, sodium carbonate, lithium carbonate, potassium phosphate, cesium fluoride, potassium hydroxide, and sodium hydroxide; the molar ratio of the compound of formula 5 to the compound of formula 4 is 1:(2.2-4); the molar ratio of the compound of formula 5 to the palladium catalyst is 1:(0.01-0.1); and the molar ratio of the compound of formula 5 to the base is 1:(3-100).
8. A method for resolving a DAD-type racemic 3D chiral fluorescent compound according to any one of claims 1 to 3, characterized in that: The splitting steps include: The DAD-type racemic 3D chiral fluorescent compound Rac-formula TM was separated into formula TMpeak1 and formula TMpeak2 by chiral high performance liquid chromatography to obtain enantiomers; 9. The method for resolving a DAD-type racemic 3D chiral fluorescent compound according to claim 8, characterized in that: The high performance liquid chromatography adopts a chiral column for separation, and the chiral column used is purchased from Daicel Pharmaceutical Chiral Technology (Shanghai) Co., Ltd., and its model is selected from one of IA, IB, IB N-5, IC, ID, IE, IF, IG, IH, IJ, IK, and IM; the mobile phase of the high performance liquid chromatography is selected from one of chromatographic n-hexane, chromatographic dichloromethane, chromatographic tetrahydrofuran, chromatographic ethyl acetate, chromatographic methanol, and chromatographic isopropanol, and a mixture of two or more of them in any proportion.
10. Use of the DAD type racemic 3D chiral fluorescent compound according to any one of claims 1 to 3 in the preparation of organic electroluminescent devices and circularly polarized luminescence.