CN109776483B - Tetraphenyl ethylene macrocyclic compound with strong fluorescence discoloration performance, and synthetic method and application thereof - Google Patents
Tetraphenyl ethylene macrocyclic compound with strong fluorescence discoloration performance, and synthetic method and application thereof Download PDFInfo
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Abstract
The invention discloses a tetraphenyl ethylene macrocyclic compound with a force-induced fluorescence color-changing performance, which is connected with an alkyl chain structural unit through a strong fluorescence property of the compound, so that the compound has the fluorescence color-changing performance before and after solid pressure increase, and can be used as a fluorescence probe to identify cyclic carboxylic acid. The structural formula of the tetraphenyl ethylene macrocyclic compound is shown as formula 1 or formula 2:
in the formula: the connecting bridge R being 1, 4-butylene (- (CH)2)4-), 2,3, 3-tetrafluoro-1, 4-butylene (-CH)2(CF2)2CH2-), 1, 5-pentylene (- (CH)2)5-), 2,3,3,4, 4-hexafluoro-1, 5-pentylene (-CH)2(CF2)3CH2-), 1, 6-hexylene (- (CH)2)6-) or 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexylene (-CH)2(CF2)4CH2‑)。
Description
Technical Field
The invention relates to the field of organic solid fluorescent mechanochromic materials, in particular to a tetraphenyl ethylene macrocyclic compound with mechanochromic performance, a synthetic method and application thereof.
Background
The conventional fluorescent molecules have reduced or even no luminescence due to their reduced fluorescence at high concentrations, thus limiting their applications in the fields of display devices, sensors, optical devices, and the like. The phenomenon that fluorescence of traditional fluorescent molecules is weakened and not luminous under the condition of aggregation is called concentration quenching effect, also called aggregation-induced fluorescence quenching (ACQ). However, the rapid development of modern technologies is a breakthrough in fluorescent materials.
In 2001, the Tang Benzhou subject group reported that some silole molecules hardly emitted light in solution, and the light emission was greatly enhanced in an aggregated state or under a solid film. Meanwhile, Aggregation Induced Emission (AIE) concepts, phenomena and mechanisms are proposed to solve the conventional fluorescent material quenching Aggregation (ACQ) problem. The AIE material has huge application potential and business opportunity in the fields of display devices, sensors, optical devices, biological imaging and the like, and has attracted research interest and attention of vast researchers. In the aggregation state, intramolecular rotation and vibration of aggregation-induced luminescent molecules are effectively suppressed. The aggregation-induced emission molecules are loosely piled up in a crystalline state, and the piled up structure is changed under the action of external force, so that the level of the original pi electron transition energy level of the molecules is influenced, and the fluorescence emission is changed to generate the piezoluminescence discoloration phenomenon.
Highlighting the color difference of the change in fluorescence, the high sensitivity of mechanical stimuli and the high intensity of solid emissions is crucial for the application of mechanical piezochromic materials. In recent years, various molecular structures having piezochromic properties have been reported, including divinylanthracene, Tetraphenylethylene (TPE), Triphenylamine (TPA), silole, and metal-organic or b-diketoboron complexes, wherein tetraphenylethylene is an important group for constructing AIE molecules.
Disclosure of Invention
The invention aims to provide a tetraphenyl ethylene macrocyclic compound with a fluorescence-induced color change performance, which is connected with an alkyl chain structural unit through a strong fluorescence property of the compound, so that the compound has a performance of increasing the fluorescence color difference before and after solid pressure. The multi-fluoroalkyl chain bridged tetraphenylethylene macrocyclic molecule can react with a guest molecule through a fluorine-hydrogen bond, so that the configuration of the tetraphenylethylene macrocyclic compound is changed, and the fluorescence change and response of the tetraphenylethylene macrocyclic compound and the guest are realized, particularly when cyclic carboxylic acid is used as the guest molecule, the fluorescence blue shift (12nm) is realized.
In order to achieve the purpose, the technical scheme provided by the invention is as follows: a tetraphenylethylene macrocyclic compound with force-induced fluorescence discoloration performance has a structural formula shown in formula 1:
in the formula: the connecting bridge R being 1, 4-butylene (- (CH)2)4-), 2,3, 3-tetrafluoro-1, 4-butylene (-CH)2(CF2)2CH2-), 1, 5-pentylene (- (CH)2)5-), 2,3,3,4, 4-hexafluoro-1, 5-pentylene (-CH)2(CF2)3CH2-), 1, 6-hexylene (- (CH)2)6-) or 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexylene (-CH)2(CF2)4CH2-)。
The invention also provides another tetraphenyl ethylene macrocyclic compound with strong fluorescence discoloration performance, and the structural formula of the tetraphenyl ethylene macrocyclic compound is shown as the formula 2:
in the formula: the connecting bridge R being 1, 4-butylene (- (CH)2)4-), 2,3, 3-tetrafluoro-1, 4-butylene (-CH)2(CF2)2CH2-), 1, 5-pentylene (- (CH)2)5-), 2,3,3,4, 4-hexafluoro-1, 5-pentylene (-CH)2(CF2)3CH2-), 1, 6-hexylene (- (CH)2)6-) or 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexylene (-CH)2(CF2)4CH2-)。
The invention also provides a synthesis method of the tetraphenylethylene macrocyclic compound, which comprises the following steps:
1) 2-bromo-1, 1, 2-triphenylethylene, 3, 5-dimethoxyphenylboronic acid, tetra-n-butylammonium bromide, potassium carbonate and Pd (PPh)3)4Dissolved in toluene, sealed, N2Washing gas, and stirring for reaction; DCM (dichloromethane) was added and the organic layer was successively washed withWashing with water and saturated saline solution, drying, and performing column chromatography to obtain TPE-OMe, namely 1,1, 2-triphenyl-2- (3, 5-dimethoxyphenyl) ethylene; the reaction formula is shown in the formula 3:
2) TPE-OMe was added to DCM and BBr was added slowly and dropwise3Stirring for reaction; adding DCM, washing the organic layer with water and saturated saline solution in sequence, drying, and carrying out column chromatography to obtain TPE-OH, namely 5- (1,2, 2-triphenylvinyl) -1, 3-benzenediol; the reaction formula is shown in the formula 4:
3) 4F-OTf ( trifluoromethanesulfonic acid 2,2,3, 3-tetrafluoro-1, 4-butylene), 6F-OTf ( trifluoromethanesulfonic acid 2,2,3,3,4, 4-hexafluoro-1, 5-pentylene), 8F-OTf ( trifluoromethanesulfonic acid 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexylene), 4R-TOs (4-methylbenzenesulfonic acid-1, 4-butylene), 6R-TOs (4-methylbenzenesulfonic acid-1, 5-pentylene) or 8R-TOs (4-methylbenzenesulfonic acid-1, 6-hexylene) with TPE-OH, potassium carbonate and acetonitrile solutions were placed in a single-neck flask, N-OTf ( trifluoromethanesulfonic acid 2,2,3, 3-tetrafluoro-1, 4-butylene), N-OTf ( trifluoromethanesulfonic acid 2,22Washing with gas, heating and refluxing for 12-24h to obtain the compounds shown in formula 1 and formula 2.
Wherein, the reaction process of 4F-OTf, 6F-OTf, 8F-OTf, 4R-TOs, 6R-TOs or 8R-TOs and TPE-OH, potassium carbonate and acetonitrile solution to obtain the compound shown in formula 1 and formula 2 is shown in figure 1.
The 4F-OTf, 6F-OTf or 8F-OTf is synthesized by the following method:
adding 2,2,3, 3-tetrafluoro-1, 4-butanediol, 2,3,3,4, 4-hexafluoro-1, 5-pentanediol or 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexanediol into 100mL DCM, cooling to 0 ℃, adding 5mL pyridine, stirring for 10 minutes, slowly dropping trifluoromethanesulfonic anhydride therein, heating to room temperature, and stirring for 12 hours. Adding 50mL of DCM for dilution, washing with water and saturated saline respectively, then drying with anhydrous sodium sulfate, and spin-drying to obtain 4F-OTf, 6F-OTf or 8F-OTf;
wherein the molar ratio of 2,2,3, 3-tetrafluoro-1, 4-butanediol, 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol or 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexanediol to trifluoromethanesulfonic anhydride is 1: 3; the reaction process is shown in the formula 5-7:
the 4R-TOs, 6R-TOs or 8R-TOs is synthesized by the following method:
adding 1, 4-butanediol, 1, 5-pentanediol or 1, 6-hexanediol and p-methylbenzenesulfonyl chloride into DCM, cooling to 0 ℃, stirring for 10 minutes, dropwise adding triethylamine, heating to room temperature after dropwise adding, and stirring for 12 hours. Adding DCM for dilution, washing with water and saturated saline respectively, then drying with anhydrous sodium sulfate, and carrying out column chromatography to obtain 4R-TOs, 6R-TOs or 8R-TOs;
wherein the molar ratio of 1, 4-butanediol, 1, 5-pentanediol or 1, 6-hexanediol to p-methylbenzenesulfonyl chloride is 1: 3; the reaction process is shown in the formula 8-10:
wherein, the 2-bromine-1, 1, 2-triphenylethylene, the 3, 5-dimethoxy phenylboronic acid, the tetra-n-butylammonium bromide, the potassium carbonate and the Pd (PPh) in the step 1)3)4The molar ratio to toluene is 1:1.5 (0.1-0.15): 3.6-4.5):0.001:6, preferably 1:1.5:0.1:3.6:0.001: 6.
Wherein, the TPE-OMe and BBr in the step 2)3The molar ratio to DCM is 1:4 (12-15), preferably 1:4: 15.
Wherein the molar ratio of the 4F-OTf, the 6F-OTf, the 8F-OTf, the 4R-TOs, the 6R-TOs or the 8R-TOs to the TPE-OH and the potassium carbonate in the step 3) is 1:1 (2-4), preferably 1:1: 2.
Wherein, the stirring reaction temperature in the step 1) is 95-97 ℃, and preferably 95 ℃; the reaction time is 12-24h, preferably 12 h.
Wherein, the drying method in the steps 1) -2) comprises the following steps: dried over anhydrous sodium sulfate.
Wherein the stirring reaction temperature in the step 2) is room temperature, and the reaction time is 8-12 h.
The invention also provides the use of the tetraphenylethylene macrocyclic compound: the tetraphenylethylene macrocyclic compound with the fluorogenic and color-changing performance is applied to the fields of sensors, fluorescent materials, display devices, optical devices and biological imaging.
Drawings
FIG. 1 is a reaction process diagram of 4F-OTf, 6F-OTf, 8F-OTf, 4R-TOs, 6R-TOs or 8R-TOs reacting with TPE-OH, potassium carbonate and acetonitrile solution to obtain compounds shown in formula 1 and formula 2;
FIG. 2 is a Differential Scanning Calorimetry (DSC) profile of Compound 4F-2;
FIG. 3 is a single crystal structural view of Compound 4F-2;
FIG. 4 is a graph showing fluorescence spectra of Compound 4F-2 in mixed solvents of water and tetrahydrofuran at different ratios;
FIG. 5 is a solid fluorescence spectrum of compound 4F-2 in different states;
FIG. 6 is a Differential Scanning Calorimetry (DSC) profile of Compound 4F-3;
FIG. 7 is a graph showing fluorescence spectra of Compound 4F-3 in a mixed solvent of water and tetrahydrofuran at different ratios;
FIG. 8 is a solid fluorescence spectrum of compound 4F-3 in different states;
FIG. 9 shows fluorescence spectra of tetrahydrofuran-water solution systems of compound 4F-3 with various carboxylic acids (hexanoic acid, cyclopentanecarboxylic acid, cyclohexanoic acid, 1-adamantanecarboxylic acid, benzoic acid);
FIG. 10 is a single crystal structural view of Compound 6R-2.
Detailed Description
The following claims are presented in further detail in connection with the detailed description of the invention, and are not to be construed as limiting the invention in any way, as any modification which comes within the scope of the claims will still fall within the scope of the invention.
Example 1
In a 250mL round bottom flask were placed 2-bromo-1, 1, 2-triphenylethylene (3.3524g,10mmol), 3, 5-dimethoxyphenylboronic acid (2.731g,15mmol), tetra-n-butylammonium bromide (0.3224g,1mmol), potassium carbonate (4.976g,36mmol, dissolved in 18mL water first) and Pd (PPh)3)4(0,01g,0.001mmol) was dissolved in 60mL of toluene, sealed, and N was added2Washing with gas for three times, and stirring and refluxing at 95 ℃ for reaction for 12 hours. After diluting with DCM, the organic layer was washed with water and saturated brine, respectively, and the organic layer was dried over anhydrous sodium sulfate. Using petroleum ether: column chromatography of ethyl acetate (V: V ═ 20:1) gave a white solid as shown in formula 11, i.e. TPE-OMe, in 98.7% yield.
Nuclear magnetic spectrum of TPE-OMe:1H NMR(600MHz,CDCl3)δ7.20–7.00(m,15H),6.25(d,J＝1.8Hz,1H),6.21(d,J＝1.8Hz,2H),3.56(s,6H).13C NMR(151MHz,CDCl3)δ＝159.95,145.52,143.91,143.57,143.24,141.07,140.90,131.31,131.25,130.96,127.76,127.64,126.50,109.67,99.24,55.18.HRMS:C28H24O2for[M]+,calculated 392.1776,found 392.1773。
example 2
TPE-OMe (3.9218g,10mmol) was added to 150mL DCM at 300mL, and 3.6mL boron tribromide (BBr)3) Slowly dropping into the mixture, heating to room temperature after dropping, and stirring for 12 h. After diluting with DCM, the organic layer was washed with water and saturated brine, respectively, and the organic layer was dried over anhydrous sodium sulfate. Using petroleum ether: and (3) carrying out column chromatography on ethyl acetate (V: 5:1) to obtain a white solid shown as a formula 12, namely TPE-OH, with the yield of 100.0%.
Nuclear magnetic spectrum of TPE-OH:1H NMR(600MHz,DMSO)δ9.00(s,2H),6.93-7.12(m,15H),5.96(s,1H),5.89(d,J＝1.3Hz,2H).13C NMR(151MHz,CDCl3)δ157.97,148.13,145.49,145.41,145.20,143.16,142.01,133.26,133.16,133.02,129.72,129.66,129.62,128.67,128.49,113.14,103.30.HRMS:C26H20O2 for[M]+,calculated 364.1463,found 364.1464。
example 3
2,2,3, 3-tetrafluoro-1, 4-butanediol (4.0000g,24.68mmol), 2,3,3,4, 4-hexafluoro-1, 5-pentanediol (5.2386g,24.68mmol), or 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexanediol (6.4667g,24.68mmol) was charged into 75mL DCM, cooled to 0 deg.C, 5mL pyridine was added thereto, stirred for 10 minutes, trifluoromethanesulfonic anhydride (12.5mL,74.04mmol) was slowly dropped thereinto, and after dropping, the temperature was raised to room temperature, and stirred for 12 hours. After diluting with DCM, the mixture was washed with water and saturated brine, respectively, and then dried over anhydrous sodium sulfate and spin-dried to obtain 4F-OTf as a white solid, 6F-OTf as an oil and 8F-OTf as a white solid, respectively, in 100.0% yield.
Nuclear magnetic spectrum of compound 4F-OTf:1H NMR(600MHz,CDCl3)δ5.06–4.60(m,4H).19F NMR(565MHz,CDCl3)δ-74.06,-120.47。
nuclear magnetic spectrum of compound 6F-OTf:1H NMR(600MHz,DMSO)δ5.50(s,4H).19F NMR(565MHz,DMSO)δ-75.14,-119.75,-124.26。
nuclear magnetic spectrum of compound 8F-OTf:1H NMR(600MHz,CDCl3)δ4.83(t,J＝12.1Hz,4H).19F NMR(565MHz,CDCl3)δ-73.95,-119.74,-122.97。
example 4
1, 4-butanediol (1.84mL,20mmol), 1, 5-pentanediol (2.08mL,20mmol) or 1, 6-hexanediol (2.3634g,20mmol) and p-toluenesulfonyl chloride (11.4390g,60mmol) were dissolved in 100mL of DCM in a 250mL round bottom flask and cooled to 0 deg.C, stirred for 10 min, triethylamine was added dropwise, and after addition, the temperature was raised to room temperature and stirred for 12 h. After diluting with DCM, the mixture was washed with water and saturated brine, respectively, and dried over anhydrous sodium sulfate. Using petroleum ether: column chromatography of ethyl acetate (V: V ═ 5:1) afforded 4R-TOs as a white solid, 6R-TOs as a white solid, and 8R-TOs as a white solid in 60.0% yield.
Nuclear magnetic spectrum of compound 4R-TOs:1H NMR(600MHz,CDCl3)δ7.78(d,J＝8.2Hz,4H),7.37(d,J＝8.1Hz,4H),4.01(t,J＝5.3Hz,4H),2.48(s,6H),1.77–1.69(m,4H)。
nuclear magnetic spectrum of compound 6R-TOs:1H NMR(600MHz,CDCl3)δ7.79(d,J＝8.3Hz,4H),7.37(d,J＝8.0Hz,4H),3.99(t,J＝6.3Hz,4H),2.48(s,6H),1.65–1.60(m,4H),1.40-1.36(m,2H)。
nuclear magnetic spectrum of compound 8R-TOs:1H NMR(400MHz,DMSO)δ7.76(d,J＝8.2Hz,4H),7.46(d,J＝7.9Hz,1H),3.94(t,J＝6.2Hz,1H),2.40(s,2H),1.46(s,1H),1.12(d,J＝19.7Hz,1H)。
example 5
4F-OTf (4.2621g,10mmol), 6F-OTf (4.7693g,10mmol), 8F-OTf (4.7621g,10mmol), 4R-TOs (3.9809g,10mmol), 6R-TOs (4.1210g,10mmol) or 8R-TOs (4.2612g,10mmol) are dissolved in 200mL of acetonitrile in a 500mL round-bottomed flask, TPE-OH (3.6415,10mmol), K2CO3(3.7642g,20mmol) and refluxed at 90 ℃ for 12 h. Acetonitrile was removed by rotary evaporation and then 100ml CH was added2Cl2After diluting with DCM, the mixture was washed with water and saturated brine, respectively, and then dried over anhydrous sodium sulfate. Using petroleum ether: ethyl acetate (V: V ═ 30:1) was subjected to column chromatography to give white solid 4F-2, white solid 4F-3, white solid 6F-2, white solid 6F-3, white solid 8F-2, white solid 8F-3, white solid 4R-2, white solid 4R-3, white solid 6R-2, white solid 6R-3, white solid 8R-2, and white solid 8R-3, respectively. The yields were 60%, 35%, 70%, 13%, 50%, 40%, 51%, 44%, 40%, 45%, 43%, 16%, respectively.
The structures of the products are as follows:
nuclear magnetic spectrum of 4F-2:1H NMR(400MHz,CDCl3)δ7.13–6.99(m,30H),6.31(d,J＝1.7Hz,4H),6.16(s,2H),4.06(s,8H).19F NMR(565MHz,CDCl3)δ-123.12.13C NMR(101MHz,CDCl3)δ157.76,146.84,143.46,142.89,142.44,142.30,139.71,131.12,127.89,126.87,114.75,112.04,100.12,65.64.HRMS:C60H44O4F8for[M]+ calculated 980.30754 ± 0.00490, found 980.31064. The single crystal structure is shown in FIG. 3.
Nuclear magnetic spectrum of 4F-3:1H NMR(600MHz,CDCl3)δ7.20–6.99(m,45H),6.34(d,J＝1.9Hz,6H),6.19(s,3H),4.08(d,J＝1.2Hz,12H).19F NMR(565MHz,CDCl3)δ-121.25.13C NMR(151MHz,CDCl3)δ158.12,146.23,143.62,143.08,142.58,142.16,139.86,131.17,127.85,126.85,115.15,112.35,102.25,65.79.HRMS:C90H66O6F12 for[M]+calculated 1470.46267±0.00735,found 1470.46623。
nuclear magnetic spectrum of 6F-2:1H NMR(600MHz,CDCl3)δ7.05–6.93(m,30H),6.23(d,J＝2.2Hz,4H),6.16(d,J＝2.0Hz,2H),4.02(t,J＝12.0Hz,8H).19F NMR(565MHz,CDCl3)δ-119.30,-126.71.13C NMR(151MHz,CDCl3)δ157.08,145.39,142.47,141.94,141.44,141.19,138.72,130.14,126.71,125.85,115.18,113.47,111.65,101.81,64.85.HRMS:C62H44O4F12 for[M]+calculated 1080.30891±0.00540,found1080.30425。
nuclear magnetic spectrum of 6F-3:1H NMR(600MHz,CDCl3)δ7.20–7.03(m,45H),6.37–6.33(m,3H),6.31(d,J＝2.3Hz,4H),4.12(t,J＝12.4Hz,12H).19F NMR(565MHz,CDCl3)δ-119.80,-125.11.13C NMR(151MHz,CDCl3)δ157.94,146.20,143.64,143.09,142.59,142.16,139.90,131.20,127.88,126.88,116.50,114.79,111.83,101.80,65.33.HRMS:C93H66O6F18 for[M]+calculated 1620.46359±0.00810,found1620.45665。
nuclear magnetic spectrum of 8F-2:1H NMR(400MHz,CDCl3)δ7.20–6.92(m,30H),6.26(d,J＝2.2Hz,4H),6.22(s,2H),4.07(t,J＝11.9Hz,8H).13C NMR(151MHz,CDCl3)δ158.30,146.74,144.07,143.49,142.97,142.71,140.26,131.64,128.21,127.38,112.74,112.35,111.59,102.68,66.24.19F NMR(565MHz,CDCl3)δ-118.82,-124.13.HRMS:C64H44O4F16 for[M]+calculated 1180.29864±0.00590,found1180.29786。
nuclear magnetic spectrum of 8F-3:1H NMR(600MHz,CDCl3)δ7.25–6.99(m,45H),6.35(t,J＝3.3Hz,9H),4.14(t,J＝12.4Hz,12H).19F NMR(565MHz,CDCl3)δ-119.46,-123.76.13C NMR(151MHz,CDCl3)δ158.00,146.32,143.62,143.07,142.56,142.23,139.84,131.20,127.90,126.90,114.64,112.32,110.95,101.82,65.60.HRMS:C96H66O6F24 for[M]+calculated 1770.44829±0.00885,found 1770.44707。
nuclear magnetic spectrum of 4R-2:1H NMR(400MHz,CDCl3)δ7.14–6.94(m,30H),6.18(t,J＝14.0Hz,6H),3.85–3.56(m,8H),1.67(s,8H).13C NMR(151MHz,CDCl3)δ159.08,145.58,143.96,143.60,140.99(d,J＝4.5),131.24,127.64,126.43,110.80,101.10,68.00,25.69.HRMS:C60H52O4 for[M+Na+]calculated 859.37365±0.00430,found 859.37578。
nuclear magnetic spectrum of 4R-3:1H NMR(600MHz,CDCl3)δ7.16–6.97(m,45H),6.26(t,J＝2.1Hz,3H),6.20(d,J＝2.1Hz,6H),3.73(t,J＝5.8Hz,12H),1.71(s,12H).13C NMR(151MHz,CDCl3)δ159.24,145.46,143.91,143.62,143.28,140.98,140.91,131.26,127.63,126.46,110.77,100.67,67.24,25.37.HRMS:C90H78O6 for[M+Na+]calculated 1277.57152±0.00639,found 1277.56906。
nuclear magnetic spectrum of 6R-2:1H NMR(600MHz,CDCl3)δ7.18–6.87(m,30H),6.25–6.10(m,6H),3.70(t,J＝6.1Hz,8H),1.60–1.54(m,8H),1.52–1.45(m,4H).13C NMR(151MHz,CDCl3)δ159.64,145.95,144.37,144.11,143.74,141.47,141.36,131.80,128.07,126.97,111.07,101.69,67.83,28.12,22.15.HRMS:C62H56O4 for[M+Na+]calculated 887.40979 ± 0.00444, found 887.40708. The single crystal structure is shown in FIG. 10.
Nuclear magnetic spectrum of 6R-3:1H NMR(600MHz,CDCl3)δ7.18–6.88(m,45H),6.24(s,3H),6.16(d,J＝1.2Hz,6H),3.67(t,J＝6.0Hz,12H),1.64–1.56(m,12H),1.50–1.42(m,6H).13C NMR(151MHz,CDCl3)δ159.43,145.41,143.95,143.67,143.33,141.04,140.94,131.28,127.62,126.40,110.21,100.68,67.69,28.71,22.85.HRMS:C93H84O6 for[M+Na+]calculated 1319.61846±0.00660,found 1319.61601。
nuclear magnetic spectrum of 8R-2:1H NMR(600MHz,CDCl3)δ7.13–6.97(m,30H),6.22(t,J＝2.2Hz,2H),6.16(d,J＝2.2Hz,4H),3.68(t,J＝6.2Hz,8H),1.64–1.60(m,8H),1.42(s,8H).13C NMR(151MHz,CDCl3)δ159.43,145.41,143.95,143.69,143.35,141.07,140.88,131.29(d,J＝8.45),127.62,126.41,110.24,100.27,67.34,28.08,25.06.HRMS:C64H60O4 for[M+Na+]calculated 915.43900±0.00458,found915.43838。
nuclear magnetic spectrum of 8R-3:1H NMR(600MHz,CDCl3)δ7.16–7.00(m,45H),6.25(t,J＝2.1Hz,3H),6.20(d,J＝2.1Hz,6H),3.70(t,J＝6.4Hz,12H),1.63(d,J＝5.9Hz,12H),1.39(s,12H).13C NMR(151MHz,CDCl3)δ160.02,146.06,144.58,144.33,143.98,141.66,141.56,131.94,128.27,127.08,111.11,101.04,68.27,29.55,26.20.HRMS:C96H90O6 for[M+Na+]calculated 1361.66172±0.00681,found 1361.66296。
example 6
The products 4F-2 and 4F-3 of example 5 were tested for their phase transition temperature by Differential Scanning Calorimetry (DSC). The products 4F-2 and 4F-3 were made up to a concentration of 1X 10 with tetrahydrofuran-3mixing the solution of mol/L with deionized water and tetrahydrofuran to obtain solution with the same concentration (1 × 10)-4) The solutions were mixed in different proportions and tested with a fluorescence spectrometer under 310nm excitation. Respectively aligning solid (solid products 4F-2 and 4F-3 (O) at room temperature) in different states under 365nm excitation by a fluorescence spectrometerriginal-RT), first grinding (Grind1-RT), standing for 4.5 hours (4.5h-RT) after first grinding, first heating the solid after first grinding to 100 ℃ and then naturally returning to room temperature (Heat1), second grinding (Grind2-RT) of the solid after first heating, and second heating the solid after second grinding to 100 ℃ and then naturally returning to room temperature (Heat2)) for testing. The products 4F-3, hexanoic acid, cyclopentanoic acid, cyclohexanoic acid, 1-adamantanecarboxylic acid and benzoic acid are respectively prepared into the concentration of 1 × 10 by using tetrahydrofuran-3The mol/L solution is prepared into 0.5 multiplied by 10 with deionized water (water: tetrahydrofuran is 9:1) concentration-4The mixed solution of mol/L is then tested by fluorescence spectroscopy under 310nm excitation. The results are as follows:
as shown in FIG. 2, the phase transition temperature of compound 4F-2 was 252.31 deg.C, and after the first milling was 250.41 deg.C.
As shown in FIG. 4, the fluorescence intensity of compound 4F-2 gradually increased with increasing proportion of deionized water (0% -90%), and a red shift was generated.
As shown in FIG. 5, Compound 4F-2 in solid form without any treatmentem431nm, first Grind (Grind1-RT) lambdaem482nm, 4.5h later (4.5 h-RT). lambda.em480nm, first Heat (Heat1) λem445nm, second Grind (Grind2-RT) lambdaem469nm, second Heat (Heat2) λem＝430nm。
As shown in FIG. 6, the phase transition temperature of compound 4F-3 was 199.71 deg.C, and after the first milling was 199.71 deg.C.
As shown in FIG. 7, the fluorescence intensity of compound 4F-3 gradually increased with increasing proportion of deionized water (0% -90%), and a red shift was generated.
As shown in FIG. 8, Compound 4F-3 in solid form without any treatmentemFirst Grind (Grind1-RT) λ at 456nmemAfter 4.5 hours (4.5 h-RT). lambda.480 nmem480nm, first Heat (Heat1) λemSecond Grind (Grind2-RT) λ 456nmem471nm, second heating (Heat2) lambdaem＝458nm。
Lambda of the compound 4F-3 solution shown in FIG. 9 without any treatmentemCompound 4F-3 mixed with hexanoic acid lambda ═ 475nmem474nm, compound 4F-3 and cyclopentanecarboxylic acid lambdaemCompound 4F-3 and cyclohexanoic acid lambda ═ 475nmemCompound 4F-3 with 1-adamantanecarboxylic acid λ ═ 475nmem461nm, Compound 4F-3 and benzoic acid Lambdaem＝475nm。
Claims (10)
1. A tetraphenylethylene macrocyclic compound with force-induced fluorescence discoloration performance is characterized in that the structural formula is shown as formula 1:
in the formula: the connecting bridge R being 1, 4-butylene (- (CH)2)4-), 2,3, 3-tetrafluoro-1, 4-butylene (-CH)2(CF2)2CH2-), 1, 5-pentylene (- (CH)2)5-), 2,3,3,4, 4-hexafluoro-1, 5-pentylene (-CH)2(CF2)3CH2-), 1, 6-hexylene (- (CH)2)6-) or 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexylene (-CH)2(CF2)4CH2-)。
2. A tetraphenylethylene macrocyclic compound with force-induced fluorescence discoloration performance is characterized in that the structural formula is shown as formula 2:
in the formula: the connecting bridge R being 1, 4-butylene (- (CH)2)4-), 2,3, 3-tetrafluoro-1, 4-butylene (-CH)2(CF2)2CH2-), 1, 5-pentylene (- (CH)2)5-), 2,3,3,4, 4-hexafluoro-1, 5-pentylene (-CH)2(CF2)3CH2-), 1, 6-hexylene (- (CH)2)6-) or 2 or a mixture of the two,2,3,3,4,4,5, 5-octafluoro-1, 6-hexylene (-CH)2(CF2)4CH2-)。
3. A process for the synthesis of the tetraphenylethylene macrocycle with mechanochromatic coloration properties according to claim 1 or 2, characterized in that it comprises the following steps:
1) 2-bromo-1, 1, 2-triphenylethylene, 3, 5-dimethoxyphenylboronic acid, tetra-n-butylammonium bromide, potassium carbonate and Pd (PPh)3)4Dissolved in toluene, sealed, N2Washing gas, and stirring for reaction; adding DCM, washing the organic layer with water and saturated saline solution in sequence, drying, and carrying out column chromatography to obtain TPE-OMe;
2) TPE-OMe was added to DCM and BBr was added slowly and dropwise3Stirring for reaction; adding DCM, washing the organic layer with water and saturated saline solution in sequence, drying, and carrying out column chromatography to obtain TPE-OH;
3) 1mol of 4F-OTf, 6F-OTf, 8F-OTf, 4R-TOs, 6R-TOs or 8R-TOs, TPE-OH, potassium carbonate and 40mL of acetonitrile solution are placed in a single-neck flask, and N is2Washing gas, heating and refluxing for 12-24h to obtain compounds shown in formula 1 and formula 2;
the 4F-OTf represents 2,2,3, 3-tetrafluoro-1, 4-butanedisulfonate; 6F-OTf represents 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol trifluoromethanesulfonate; 8F-Otf represents trifluoromethanesulfonic acid 2,2,3,3,4,4,5, 5-octafluoro-1, 6-hexanediol; 4R-Tos represents 4-methylbenzenesulfonic acid-1, 4-butanediyl ester; 6R-TOs represents 4-methylbenzenesulfonic acid-1, 5-pentanediol; 8R-TOs represents 4-methylbenzenesulfonic acid-1, 6-hexanediol; the structure of TPE-OH is:
4. the method for synthesizing tetraphenylethylene macrocycle having mechanochromatic properties according to claim 3, wherein said 2-bromo-1, 1, 2-triphenylethylene, 3, 5-dimethoxyphenylboronic acid, tetra-n-butylammonium bromide, potassium carbonate, Pd (PPh) in step 1)3)4The molar ratio of the toluene to the toluene is 1:1.5:(0.1-0.15):(3.6-4.5):0.001:6。
5. The method for synthesizing tetraphenylethylene macrocycles with fluorogenic coloration properties according to claim 3, characterized in that step 2) said TPE-OMe, BBr3The molar ratio to DCM was 1:4 (12-15).
6. The method for synthesizing the tetraphenylethylene macrocycle with strong fluorogenic color-changing property of claim 3, wherein the molar ratio of 4F-OTf, 6F-OTf, 8F-OTf, 4R-TOs, 6R-TOs or 8R-TOs to TPE-OH and potassium carbonate in step 3) is 1:1 (2-4).
7. The method for synthesizing the tetraphenylethylene macrocycle with the fluorogenic color-changing property of claim 3, wherein the stirring reaction temperature of step 1) is 95-97 ℃ and the reaction time is 12-24 h.
8. The method for synthesizing the tetraphenylethylene macrocycle with strong fluorogenic coloration properties according to claim 3, characterized in that said drying method of steps 1) -2) is: dried over anhydrous sodium sulfate.
9. The method for synthesizing the tetraphenylethylene macrocycle with the fluorogenic color-changing property of claim 3, wherein said stirring reaction temperature of step 2) is room temperature and the reaction time is 8-12 h.
10. Use of the tetraphenylethylene macrocycle with fluorogenic coloration properties according to claim 1 or 2 in the fields of sensors, fluorescent materials, display devices, optical devices and biological imaging.
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