CN114751811A - Axial chiral solid-state fluorescent material with spiroalkene structure - Google Patents

Axial chiral solid-state fluorescent material with spiroalkene structure Download PDF

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CN114751811A
CN114751811A CN202210522428.7A CN202210522428A CN114751811A CN 114751811 A CN114751811 A CN 114751811A CN 202210522428 A CN202210522428 A CN 202210522428A CN 114751811 A CN114751811 A CN 114751811A
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helicene
binol
solid
fluorescent material
axial chiral
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陈绍晋
胡志强
刘春芳
原春鸣
贾柯
刘晶
王鲲鹏
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Qingdao University of Science and Technology
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Abstract

The invention discloses an axial chiral solid fluorescent material with a helicene structure, and belongs to the technical field of fluorescent materials. The axial chiral solid fluorescent compound provided by the invention has the characteristics of an axial chiral structure and a spiroalkene structure. The solid fluorescent compound can emit bright blue fluorescence in an organic solvent and in a solid state, and has high fluorescence quantum yield. The enantiomer of the fluorescent compound has obvious circular dichroism, and can show circular polarization luminescence property after being excited. The axial chiral fluorescent material disclosed by the invention has excellent solid-state fluorescence luminous efficiency and chiral optical performance, and has potential application value in the photoelectric field.

Description

Axial chiral solid fluorescent material with spiroalkene structure
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of fluorescent materials, and particularly relates to an axial chiral solid fluorescent material with a helicene structure.
[ background of the invention ]
The chiral fluorescent functional material has wide application prospect in the aspects of optical detectors, biological probes, three-dimensional optical display, optical storage devices, photoelectric devices and the like (Acta Chim. Sinica,2017,75, 1150-containing material 1163). The chiral organic luminescent material is an important chiral fluorescent functional material, and has the characteristics of easy derivatization of molecular structure, high molecular luminescent efficiency, multiple molecular species and the like. Currently, researchers have developed various chiral organic light emitting materials, which can be classified into central chirality (org. lett.,2016,18, 2719-. Chiral organic light emitting materials that have been developed may exhibit excellent light emitting efficiency and a high light emitting asymmetry factor in solution, but the fluorescence quantum yield in the solid state or thin film state is generally low. However, in many practical applications, the chiral organic fluorescent functional molecule needs to be prepared into a thin film or a solid material. The practical application of the chiral organic light-emitting material is limited to a great extent due to the defect of low solid-state fluorescence light-emitting efficiency. Therefore, there is a need to design and synthesize a novel chiral organic fluorescent material having high solid-state fluorescence luminous efficiency.
[ summary of the invention ]
The invention aims to provide an axial chiral solid fluorescent material with a helicene structure.
The invention is realized by the following technical scheme:
an axial chiral solid-state fluorescent material with a spiroalkene structure has a structural formula shown as a formula I:
Figure BDA0003642218390000011
in the formula R1Is aryl, R2Is methyl, ethyl or n-propyl.
Preferably, R in the structural formula1Is at least one of phenyl, 4-methoxyphenyl, 4-pyridyl and 4-cyanophenyl.
The axial chiral solid-state fluorescent material can be a levorotatory solid-state fluorescent material, a dextrorotatory solid-state fluorescent material or a racemic solid-state fluorescent material.
The preparation reaction formula of the axial chiral solid fluorescent material is as follows:
Figure BDA0003642218390000021
the method specifically comprises the following steps:
a. under the alkaline condition, binaphthol-3-aldehyde protected by methoxymethyl reacts with 4-bromobenzyl triphenyl phosphonium bromide at 0-60 ℃ for 2-12h to obtain an olefin compound 2;
b. reacting the obtained olefin compound 2 for 6-12h under the illumination condition to obtain a bromo [4] spiroalkene compound 3;
c. under the acidic condition, the bromo [4] helicene compound 3 is hydrolyzed at 0-60 ℃ to remove a methoxymethyl protecting group, and then reacts with methyl iodide under the alkaline condition to generate a methyl-protected [4] helicene compound 4;
d. in the mixed solvent of DMF and triethylamine, compound 4 and aryl ethylene react for 6-18h at 60-120 deg.c under the catalysis of palladium catalyst to produce BINOL 4 helicene as one axial chiral solid fluorescent compound.
The fluorescent compound provided by the invention has the characteristics of axial chiral structure and spiroalkene structure, can emit blue fluorescence in an organic solvent and in a solid state, and has higher absolute fluorescence quantum yield. The enantiomer of the fluorescent compound shows an obvious Compton effect in circular dichroism chromatography, and can show circular polarization luminescence property after being excited.
[ description of the drawings ]
FIG. 1 is a nuclear magnetic hydrogen spectrum of the compound BINOL [4] helicene-1 prepared in example 1.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the compound BINOL 4 helicene-2 prepared in example 2.
FIG. 3 shows the UV absorption spectrum of BINOL 4 helicene-1 prepared in example 1 in DMSO.
FIG. 4 shows the fluorescence emission spectrum of BINOL 4 helicene-1 prepared in example 1 in DMSO.
FIG. 5 shows the fluorescence emission spectrum of BINOL 4 helicene-1 prepared in example 1 in the solid state.
FIG. 6 is a chromatogram of BINOL [4] helicene-1, a compound prepared in example 1.
[ detailed description ] embodiments
The present invention is further illustrated by the following specific examples, but the present invention is not limited to the following examples.
Example 1 Synthesis of the Compounds (R) -BINOL [4] helicene-1 and (S) -BINOL [4] helicene-1
The reaction formula is as follows:
Figure BDA0003642218390000031
1) to a 100ml round bottom flask was added 3.2g (7.95mmol) of (R) -2,2 '-bis (methoxymethoxy) - [1,1' -binaphthyl ] -3-aldehyde, 4.4g (8.57mmol) of 4-bromobenzyl triphenyl phosphonium bromide, and 40ml of anhydrous tetrahydrofuran under ice-bath conditions. After the reaction mass was completely dissolved, 5.9g (61.4mmol) of sodium tert-butoxide was added in portions to the reaction solution and reacted for 4 hours under ice bath conditions. The reaction was quenched with water, dichloromethane was added to the reaction solution, and the organic phase obtained by separation was dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography to obtain 4.1g of (R, E) -3- (4-bromostyryl) -2,2 '-bis (methoxymethoxy) -1,1' -binaphthyl in 95% yield.
2) To a quartz tube were added 0.2g (0.36mmol) of (R, E) -3- (4-bromostyryl) -2,2 '-bis (methoxymethoxy) -1,1' -binaphthyl, 0.3ml (4.29mmol) of ethylene oxide, 0.15g (0.59mmol) of iodine and 150ml of dichloromethane under a nitrogen atmosphere. The reaction solution was reacted for 6 hours under light (500W high-pressure mercury lamp). The reaction was quenched by addition of sodium sulfite solution. The organic phase is separated, dried and separated by column chromatography to obtain 0.18g of (R) -2-bromo-7- (methoxymethyloxy) -8- (2- (methoxymethyloxy) naphthalen-1-yl) benzo [ c ] phenanthrene with a yield of 90%.
3) To a 100ml round bottom flask were added 0.5g (0.90mmol) of (R) -2-bromo-7- (methoxymethyloxy) -8- (2- (methoxymethyloxy) -1-naphthyl) benzo [ c ] phenanthrene and 30ml of tetrahydrofuran. The reaction solution was cooled to 0 ℃ and 2ml of concentrated hydrochloric acid was added, followed by reaction at room temperature for 5 hours. Aqueous sodium bicarbonate was added to neutralize the hydrochloric acid, and then dichloromethane was added to the solution, followed by liquid separation and spin drying of the organic phase to obtain an oily intermediate. The product was dissolved in 40ml of anhydrous DMF and the solution was cooled to 0 ℃ and 0.19g (7.92mmol, content 55%) of sodium hydride was added in portions. After stirring until no more bubbles were formed in the solution, 0.38g (2.70mmol) of methyl iodide was added. And reacting for 1h at room temperature under the protection of nitrogen. The reaction was quenched by the addition of ethanol, followed by the addition of dichloromethane, liquid separation, drying of the organic phase over anhydrous sodium sulfate and spin drying to give 0.39g of (R) -2-bromo-7-methoxy-8- (2- (methoxy) naphthalen-1-yl) benzo [ c ] phenanthrene, 88% yield.
4) 300mg (0.60mmol) of (R) -2-bromo-7-methoxy-8- (2- (methoxy) naphthalen-1-yl) benzo [ c ] was added to a 100ml three-necked flask under nitrogen protection]Phenanthrene, 24mg (0.11mmol) palladium acetate and 82.5mg (0.27mmol) tri-o-methylphenyl phosphine, followed by addition of 25ml anhydrous DMF and 20ml triethylamine. The solution was warmed to 45 ℃ for 0.5h and 75mg (0.72mmol) of styrene was added. Then the solution is heated to 115 ℃ for reaction for 5 h. DMF and triethylamine were removed by rotary evaporation and dichloromethane was added to the solution. The organic phase is washed with water, dried and subjected to column chromatography to obtain 0.25g of (R, E) -7-methoxy-8- (2-methoxynaphthalene-1)-yl) -2-styrylbenzo [ c]Phenanthrene (R) -BINOL [4]]helicene-1, 81% yield.1H NMR(500MHz,CDCl3)δ9.21(s,1H),9.16(d,J＝8.5Hz,1H),8.26(d,J＝8.7Hz,1H),8.04(dd,J＝8.7,3.0Hz,2H),7.95(d,J＝8.7Hz,1H),7.92–7.89(m,2H),7.64–7.60(m,3H),7.51(d,J＝9.1Hz,1H),7.44–7.33(m,6H),7.33–7.29(m,2H),7.23(d,J＝3.4Hz,2H),3.80(s,3H),3.55(s,3H).13C NMR(126MHz,CDCl3)δ154.1,151.4,136.4,134.2,133.1,132.8,132.1,129.6,128.9,128.3,128.3,128.2,128.1,127.9,127.7,127.6,127.3,127.1,127.0,127.0,126.7,126.5,126.2,126.1,125.7,125.6,125.2,125.1,125.1,124.3,123.9,122.7,122.5,122.3,120.0,118.2,112.6,60.4,55.6.HRMS(ESI):calcd.for C38H28O2Na[M+Na]+:539.1982,found:539.1991.Optical rotation:[α]D 16＝-45.3(c＝0.10,ethyl acetate)。
The compound (S, E) -7-methoxy-8- (2-methoxynaphthalen-1-yl) -2-styrylbenzo [ c]Phenanthrene (S) -BINOL [4]]The helicene-1 can be (S) -2,2 '-bis (methoxymethoxy) - [1,1' -binaphthyl]The-3-aldehyde is prepared by the synthesis steps. The (S) form of the product has the same nuclear magnetic and mass spectral data as the (R) form of the product. Optical rotation [ alpha ]]D 16＝+79(c＝0.10,ethyl acetate)。
Mixing equal amounts of (R) -BINOL [4] helicene-1 and (S) -BINOL [4] helicene-1 to obtain BINOL [4] helicene-1 racemate.
Example 2 Synthesis of the Compounds (R) -BINOL [4] helicene-2 and (S) -BINOL [4] helicene-2
The reaction formula is as follows:
Figure BDA0003642218390000041
300mg (0.60mmol) of (R) -2-bromo-7-methoxy-8- (2- (methoxy) naphthalen-1-yl) benzo [ c ] was added to a 100ml three-necked flask under nitrogen protection]Phenanthrene, 24mg (0.11mmol) palladium acetate and 82.5mg (0.27mmol) tris-o-methylphenylphosphine, then 25ml anhydrous DMF and 20ml triethylamine are added. The solution was warmed to 45 ℃ for 0.5h and 93mg (0.72mmol) of 4-vinylbenzyl were addedA nitrile. Then the solution is heated to 115 ℃ for reaction for 5 h. DMF and triethylamine were removed by rotary evaporation and dichloromethane was added to the solution. The organic phase is washed with water, dried and subjected to column chromatography to give 0.19g of (R, E) -4- (2- (7-methoxy-8- (2-methoxynaphthalen-1-yl) benzo [ c ]]Phenanthren-2-yl) vinyl) benzonitrile (R) -BINOL [4]helicene-2, 64% yield.1H NMR(500MHz,CDCl3)δ9.22(s,1H),9.11(d,J＝8.5Hz,1H),8.30(d,J＝8.7Hz,1H),8.06(d,J＝8.8Hz,2H),7.96(d,J＝8.7Hz,1H),7.89–7.91(m,2H),7.66(s,4H),7.64–7.60(m,1H),7.52–7.49(m,2H),7.39(d,J＝3.1Hz,2H),7.35–7.30(m,2H),7.25–7.22(m,2H),3.81(s,3H),3.56(s,3H).13C NMR(126MHz,CDCl3)δ154.1,151.4,136.4,134.1,133.1,132.8,132.1,129.6,128.9,128.3,128.2,128.1,127.9,127.8,127.5,127.3,127.1,127.0,127.0,126.7,126.6,126.5,126.2,125.7,125.6,125.5,125.1,125.1,125.1,124.3,123.9,122.7,122.5,122.4,120.0,118.2,112.6,60.4,55.6.HRMS(ESI):calcd.for C39H27NO2Na[M+Na]+:564.1934,found:564.1939.Optical rotation:[α]D 16＝-95.3(c＝0.10,ethyl acetate)。
The compound (S, E) -4- (2- (7-methoxy-8- (2-methoxynaphthalen-1-yl) benzo [ c)]Phenanthren-2-yl) vinyl) benzonitrile (S) -BINOL [4]The helicene-2 can be (S) -2-bromo-7-methoxy-8- (2- (methoxy) naphthalen-1-yl) benzo [ c]Phenanthrene is used as a raw material and is prepared according to the synthesis steps. The (S) form of the product has the same nuclear magnetic and mass spectral data as the (R) form of the product. Optical rotation [ alpha ]]D 16＝+108.7(c＝0.10,ethyl acetate)。
Mixing equal amounts of (R) -BINOL 4-helicene-2 and (S) -BINOL 4-helicene-2 to obtain BINOL 4-helicene-2 racemate.
Example 3 Synthesis of the Compounds (R) -BINOL [4] helicene-3 and (S) -BINOL [4] helicene-3
The reaction formula is as follows:
Figure BDA0003642218390000051
under the protection of nitrogen, 30 parts of a mixture is added into a 100ml three-neck flask0mg (0.60mmol) of (R) -2-bromo-7-methoxy-8- (2- (methoxy) naphthalen-1-yl) benzo [ c]Phenanthrene, 24mg (0.11mmol) palladium acetate and 82.5mg (0.27mmol) tri-o-methylphenyl phosphine, followed by addition of 25ml anhydrous DMF and 20ml triethylamine. The solution was warmed to 45 ℃ for 0.5h and 97mg (0.72mmol) of 4-methoxystyrene was added. Then the solution is heated to 115 ℃ for reaction for 5 h. DMF and triethylamine were removed by rotary evaporation and dichloromethane was added to the solution. The organic phase is washed with water, dried by spinning and subjected to column chromatography to obtain 0.20g of (R, E) -7-methoxy-8- (2-methoxynaphthalen-1-yl) -2- (4-methoxystyryl) benzo [ c)]Phenanthrene (R) -BINOL [4]]helicene-3, 62% yield.1H NMR(500MHz,CDCl3)δ9.17(d,J＝8.8Hz,2H),8.24(d,J＝8.6Hz,1H),8.06–8.02(m,2H),7.95(d,J＝8.7Hz,1H),7.90(dd,J＝7.9,5.6Hz,2H),7.62(ddd,J＝8.2,5.6,2.5Hz,1H),7.55(d,J＝8.7Hz,2H),7.51(d,J＝9.2Hz,1H),7.38–7.37(m,2H),7.35–7.31(m,1H),7.28(s,2H),7.23(d,J＝3.5Hz,2H),6.94(d,J＝8.7Hz,2H),3.85(s,3H),3.81(s,3H),3.56(s,3H).13C NMR(126MHz,CDCl3)δ158.4,154.1,151.5,134.5,133.1,132.8,131.9,129.7,129.3,128.9,128.7,128.2,128.2,127.8,127.2,127.0,126.9,126.8,126.2,126.1,126.0,125.7,125.2,125.1,124.3,123.8,122.7,122.4,122.3,119.8,118.3,113.2,112.7,60.3,55.6,54.3.HRMS(ESI):calcd.for C39H30O3Na[M+Na]+:569.2088,found:569.2089.Optical rotation:[α]D 16＝-55.3(c＝0.10,ethyl acetate)。
The compound (S, E) -7-methoxy-8- (2-methoxynaphthalen-1-yl) -2- (4-methoxystyryl) benzo [ c]Phenanthrene (S) -BINOL [4]]The helicene-3 can be (S) -2-bromo-7-methoxy-8- (2- (methoxy) naphthalen-1-yl) benzo [ c]Phenanthrene is used as a raw material and is prepared according to the synthesis steps. The (S) form of the product has the same nuclear magnetic and mass spectral data as the (R) form of the product. Optical rotation [ alpha ]]D 16＝+112.7(c＝0.10,ethyl acetate)。
Mixing equal amounts of (R) -BINOL [4] helicene-3 and (S) -BINOL [4] helicene-3 to obtain BINOL [4] helicene-3 racemate.
Example 4 Synthesis of the Compounds (R) -BINOL [4] helicene-4 and (S) -BINOL [4] helicene-4
The reaction formula is as follows:
Figure BDA0003642218390000061
300mg (0.60mmol) of (R) -2-bromo-7-methoxy-8- (2- (methoxy) naphthalen-1-yl) benzo [ c ] was added to a 100ml three-necked flask under nitrogen protection]Phenanthrene, 24mg (0.11mmol) palladium acetate and 82.5mg (0.27mmol) tri-o-methylphenyl phosphine, followed by addition of 25ml anhydrous DMF and 20ml triethylamine. The solution was warmed to 45 ℃ for 0.5h and 76mg (0.72mmol) of 4-vinylpyridine was added. Then the solution is heated to 115 ℃ for reaction for 5 h. DMF and triethylamine were removed by rotary evaporation and dichloromethane was added to the solution. The organic phase is washed with water, dried and subjected to column chromatography to give 0.22g of (R, E) -4- (2- (7-methoxy-8- (2-methoxynaphthalen-1-yl) benzo [ c ]]Phenanthren-2-yl) vinyl) pyridine (R) -BINOL [4]]helicene-4, 70% yield.1H NMR(500MHz,CDCl3)δ9.23(s,1H),9.12(d,J＝8.5Hz,1H),8.62(s,2H),8.30(d,J＝8.6Hz,1H),8.06(dd,J＝8.7,2.5Hz,2H),7.96(d,J＝8.7Hz,1H),7.91(d,J＝8.3Hz,2H),7.65–7.58(m,2H),7.51(d,J＝9.1Hz,1H),7.46(d,J＝3.4Hz,2H),7.40–7.39(m,2H),7.35–7.32(m,1H),7.23–7.20(m,3H),3.81(s,3H),3.56(s,3H).13C NMR(126MHz,CDCl3)δ154.1,151.4,149.2,143.7,133.1,132.9,132.8,132.7,129.6,129.0,128.3,128.1,128.1,127.6,127.0,126.9,126.2,126.1,125.8,125.3,125.3,124.2,124.0,122.7,122.6,122.5,120.7,120.0,118.1,112.6,60.4,55.6.HRMS(ESI):calcd.for C37H28NO2[M+H]+:518.2120,found:518.2117.Optical rotation:[α]D 16＝-69(c＝0.10,ethyl acetate)。
The compound (S, E) -4- (2- (7-methoxy-8- (2-methoxynaphthalen-1-yl) benzo [ c ]]Phenanthren-2-yl) vinyl) pyridine (S) -BINOL [4]]The helicene-4 can be (S) -2-bromo-7-methoxy-8- (2- (methoxy) naphthalen-1-yl) benzo [ c]Phenanthrene is used as a raw material and is prepared according to the synthesis steps. The product of type (S) has the same nuclear magnetic and mass spectral data as the product of type (R). Optical rotation [ alpha ]]D 16＝+67.3(c＝0.10,ethyl acetate)。
Mixing equal amounts of (R) -BINOL 4-helicene-4 and (S) -BINOL 4-helicene-4 to obtain BINOL 4-helicene-4 racemate.
Example 5: the optical properties of the compounds BINOL 4 helicene-1, BINOL 4 helicene-2, BINOL 4 helicene-3 and BINOL 4 helicene-4 prepared in examples 1 to 4 were investigated by ultraviolet, fluorescence, circular dichroism and circular polarized light emission.
The maximum absorption wavelengths of the compounds BINOL 4 helicene-1, BINOL 4 helicene-2, BINOL 4 helicene-3 and BINOL 4 helicene-4 in DMSO solutions are 315nm, 320nm, 304nm and 315nm respectively. The compounds BINOL 4 helicene-1, BINOL 4 helicene-2, BINOL 4 helicene-3 and BINOL 4 helicene-4 can emit bright blue fluorescence in DMSO solution, and their maximum emission wavelengths are 409nm, 441nm, 435nm and 436nm respectively. The fluorescence quantum yields of the compounds BINOL 4 helicene-1, BINOL 4 helicene-2, BINOL 4 helicene-3 and BINOL 4 helicene-4 in DMSO solutions were 38.8%, 28.3%, 45.0% and 26.5%, respectively. In the solid state, the fluorescence emission wavelengths of the compounds BINOL 4 helicene-1, BINOL 4 helicene-2, BINOL 4 helicene-3 and BINOL 4 helicene-4 are 450nm, 458nm, 462nm and 496nm, respectively. The absolute fluorescence quantum yields of the compounds BINOL 4 helicene-1, BINOL 4 helicene-2, BINOL 4 helicene-3 and BINOL 4 helicene-4 in the solid state were found to be 38.7%, 54.1%, 67.7% and 2.9%, respectively, according to the integrating sphere technique.
Compound BINOL [4]]helicene-1、BINOL[4]helicene-2、BINOL[4]helicene-3 and BINOL [4]]The circular dichroism signals of the (R) and (S) enantiomers of helicene-4 are respectively in mirror image relationship. In circular dichroism, these compounds showed strong Compton effects at 275nm and 320 nm. Compound BINOL [4]]The (R) type and (S) type enantiomers of helicene-4 have circular polarized luminescence properties with asymmetric luminescence factors of-1.4X 10-4And 2.7X 10-4。
The foregoing is merely a preferred embodiment of this invention, which is intended to be illustrative, not limiting; it will be understood by those skilled in the art that many changes, modifications and equivalents may be made within the scope of the invention as defined in the claims, and all such changes and modifications may be made without departing from the invention.

Claims (3)

1. An axial chiral solid-state fluorescent material with a spiroalkene structure is characterized in that the structural formula of the solid-state fluorescent material is shown as formula I:
Figure FDA0003642218380000011
wherein R is1Is aryl, R2Is methyl, ethyl or n-propyl.
2. The axial chiral solid state phosphor of claim 1, wherein said solid state phosphor is a levorotatory solid state phosphor, or a dextrorotatory solid state phosphor, or a racemic solid state phosphor.
3. The axial chiral solid state fluorescent material of claims 1-2, wherein: in the structural formula, R1Is any one of phenyl, 4-methoxyphenyl, 4-pyridyl and 4-cyanophenyl.
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