主链含单羟基硼酸高分子的制备与聚集诱导发光性能
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摘要
通过1, 2-二(4-溴苯)-1, 2-二苯乙烯的格氏试剂和硼酸三甲酯的缩聚反应合成了四苯乙烯和硼在主链的首个单羟基硼酸共轭高分子(PTPEBA)。利用核磁共振氢谱和傅里叶变换红外光谱进行了结构鉴定。凝胶渗透色谱测试表明制备的PTPEBA数均相对分子质量为5200。通过荧光发射光谱和荧光量子产率研究了PTPEBA在不同体积分数THF/H_2O体系中的聚集诱导发光(AIE)效应。结果表明,当水体积分数大于80%时,体系表现出明显的AIE特性;在水中体系荧光强度是在THF溶液中强度的477倍。利用荧光发射光谱对PTPEBA与酸性红-87、荧光素染料(质量分数1%)掺杂进行分析,发现PTPEBA可以使二者的固态荧光增强,此发现有望成为一种使商业染料固态发光的新方法。
The first conjugated borinic acid polymer(PTPEBA) featured with tetraphenylethylene unit and boron in the main chain was synthesized by polycondensation reaction of the Grignard reagent of 1,2-bis(4-bromophenyl)-1,2-diphenylethene and trimethyl borate. It was characterized by ~1H-NMR and FT-IR. Gel permeation chromatography(GPC) result indicates that the number average molecular weight of PTPEBA is 5200. The aggregation-induced emission(AIE) of PTPEBA in THF/H_2O mixture was investigated by fluorescence emission spectra and fluorescence quantum yield. The results demonstrate that PTPEBA exhibits obvious AIE feature when the volume fraction of water is higher than 80% and the fluorescence intensity in water is 477 times greater than that in THF. Fluorescence emission spectra were used to study the doping between PTPEBA and tiny amount(1%) of readily available ACQ fluorescent dyes(acid red 87 and fluorescein). The results show that AIE PTPEBA causes the luminescence enhancement of fluorescent dyes(acid red 87 and fluorescein) in solid state, which is a promising method for enhancing the luminescence of commercial ACQ fluorescent dyes in solid state.
The first conjugated borinic acid polymer(PTPEBA) featured with tetraphenylethylene unit and boron in the main chain was synthesized by polycondensation reaction of the Grignard reagent of 1,2-bis(4-bromophenyl)-1,2-diphenylethene and trimethyl borate. It was characterized by ~1H-NMR and FT-IR. Gel permeation chromatography(GPC) result indicates that the number average molecular weight of PTPEBA is 5200. The aggregation-induced emission(AIE) of PTPEBA in THF/H_2O mixture was investigated by fluorescence emission spectra and fluorescence quantum yield. The results demonstrate that PTPEBA exhibits obvious AIE feature when the volume fraction of water is higher than 80% and the fluorescence intensity in water is 477 times greater than that in THF. Fluorescence emission spectra were used to study the doping between PTPEBA and tiny amount(1%) of readily available ACQ fluorescent dyes(acid red 87 and fluorescein). The results show that AIE PTPEBA causes the luminescence enhancement of fluorescent dyes(acid red 87 and fluorescein) in solid state, which is a promising method for enhancing the luminescence of commercial ACQ fluorescent dyes in solid state.
引文
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[3]Dong Y,Lam J W Y,Qin A,et al.Aggregation-induced emissions of tetraphenylethene derivatives and their utilities as chemical vapor sensors and in organic light-emitting diodes[J].Appl.Phys.Lett.,2007,91:011111.
[4]Qi Q,Liu Y,Fang X,et al.AIE(AIEE)and mechanofluorochromic performances of TPE-methoxylates:effects of single molecular conformations[J].Rsc Adv.,2013,3:7996-8002.
[5]Ding D,Li K,Liu B,et al.Bioprobes based on AIE fluorogens[J].Acc.Chem.Res.,2013,46:2441-2453.
[6]Ja?kle F.Advances in the synthesis of organoborane polymers for optical,electronic,and sensory applications[J].Chem.Rev.,2010,110:3985-4022.
[7]Cambre J N,Sumerlin B S.Biomedical applications of boronic acid polymers[J].Polymer,2011,52:4631-4643.
[8]Wan W M,Cheng F,J?kle F.A borinic acid polymer with fluoride ion-and thermo-responsive properties that are tunable over a wide temperature range[J].Angew.Chem.Int.Ed.,2014,53:8934-8938.
[9]Cheng F,Wan W M,Zhou Y,et al.Borinic acid block copolymers:new building blocks for supramolecular assembly and sensory applications[J].Polym.Chem.,2015,6:4650-4656.
[10]Lu P,Lam J W Y,Liu J,et al.Regioselective alkyne polyhydrosilylation:synthesis and photonic properties of poly(silylenevinylene)s[J].Macromolecules,2011,44:5977-5986.
[11]Dong Y,Lam J W Y,Qin A,et al.Aggregation-induced and crystallization-enhanced emissions of 1,2-diphenyl-3,4-bis(diphenylmethylene)-1-cyclobutene[J].Chem.Commun.,2007(31):3255-3257.
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