苯并噻吩稠合双硼荧光染料的手性光学性质及组装手性放大研究  

Chiroptical properties and assembled chiral amplification in benzothieno-fused bisboron fluorescent dyes

作　　者：孙营柱 于长江[1] 焦莉娟[1] 徐瑞明 郝二红[1] 李家柱[2] 刘鸣华[3] Yingzhu Sun;Changjiang Yu;Lijuan Jiao;Ruiming Xu;Erhong Hao;Jiazhu Li;Minghua Liu(Key Laboratory of Functional Molecular Solids,Ministry of Education,School of Chemistry and Materials Science,Anhui Normal University,Wuhu 241002,China;College of Chemistry and Chemical Engineering,Yantai University,Yantai 264005,China;Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China)

机构地区：[1]功能分子固体教育部重点实验室,安徽师范大学化学与材料科学学院,芜湖241002 [2]烟台大学化学化工学院,烟台264005 [3]中国科学院化学研究所,北京100190

出　　处：《中国科学：化学》2024年第8期1352-1360,共9页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:22271002);安徽省自然科学基金(编号:2008085QB67,2308085J14);安徽省高校科研(编号:2023AH050149);安徽省博士后研究人员科研活动(编号:2021B533)资助项目。

摘　　要：近年来,基于有机硼的手性发光材料因具有其独特结构和性质备受关注.本研究在吡咯吡啶腙肼双硼荧光团(BOPPY)上同时引入了苯并噻吩和手性胺侧链,成功构建了一种新型苯并噻吩稠环手性BOPPY.相对于手性母体,苯并噻吩稠环的导入实现了其圆二色(CD)和圆偏振发光(CPL)光谱分别红移50和70 nm,同时伴随手性旋向的反转.此外,手性BOPPY分子在有机溶剂中展现出镜像的CD、明亮的黄绿色CPL(Φ_(F)=0.37,540 nm,g_(lum)=1×10^(-4))、高摩尔吸光系数、大斯托克斯位移、良好的热稳定性,以及荧光量子产率高达25%的强薄膜固态发射(538 nm,g_(lum)=7.4×10^(-4)).更有趣的是,手性BOPPY分子在水中表现出聚集诱导荧光增强活性,其在表面活性剂作用下进行共组装的超分子体系显示出手性放大行为,得到的聚集体表现出显著增强的圆偏振发光性质(566 nm,g_(lum)=0.069),组装体g_(lum)相比于其分子态提升了690倍.推测手性放大机制可能是手性BOPPY分子和表面活性剂在弱相互作用协同驱动进行各向异性调节,从而构建了有序的手性纳米结构.In recent years, organoboron chiral fluorescent materials have attracted extensive attention due to their unique structure and properties. This study successfully constructed a novel chiral benzothieno-fused BOPPY by grafting both benzothiophene and chiral amine side chains onto the BOPPY scaffold. Compared with the chiral parent molecule, the fusion of benzothiophene resulted in 50 and 70 nm bathochromic shifts of the circular dichroism(CD) and circularly polarized luminescence(CPL) spectra, respectively, simultaneously accompanied by a reversal in the direction. Furthermore, this chiral BOPPYexhibited mirror-image CD and bright yellow-green CPL(Φ_(F)= 0.37, 540 nm,g_(lum)= 1 × 10^(-4)), good thermal stability, and strong thin film solid-state emission with a fluorescence quantum yield of up to 25%(538 nm, │g_(lum)│= 7.4 × 10^(-4)). Interestingly, it showed aggregation-induced emission in water and chiral amplification behavior(566 nm, glum= 0.069) in supramolecular systems co-assembled with surfactants, with an enhancement of glumby 690 times compared to its molecular state. The amplification mechanism is speculated to involve the synergistic modulation of weak interactions between chiral BOPPYs and SDS surfactants, leading to the formation of ordered chiral nanostructures.

关 键 词：圆偏振发光 双硼荧光染料 聚集诱导发光 超分子组装 手性放大 

分 类 号：O641.3[理学—物理化学] TQ617.3[理学—化学]