Department of Chemical Sciences, Indian Institute of Science, Education and Research (IISER) Mohali, Punjab, 140306, India.
Chemistry. 2019 Nov 22;25(65):14870-14880. doi: 10.1002/chem.201902952. Epub 2019 Oct 28.
Regioisomeric acceptor-donor (AD) molecular rotors (p-AD, m-AD and m-ADA) were synthesized and characterized, wherein dyads p-AD and m-AD, and triad m-ADA contained 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) and benzodithiophene (BDT) as electron-acceptor and electron-donor, respectively. In all the compounds, the donor and acceptor moieties are electronically decoupled by a phenyl spacer, either through a para coupling or through a meta coupling. The dyad counterparts p-AD and m-AD showed distinct photophysical characteristics in which dyad p-AD showed TICT band at ca. 654 nm characterized by a Stokes shift of ca. 150 nm and prominent solvatochromism. However, meta regioisomeric triad m-ADA showed well-defined aggregation in solution. Notably, because of the temperature-tunable and solvent-viscosity-dependent emission, efficient ratiometric temperature sensing with positive and negative temperature coefficients and viscosity sensing was observed for all compounds. Interestingly, the fluorescence of dyad m-AD (in 10/90 v/v THF/water) revealed a near-white light emission with CIE chromaticity coordinates (x, y) of (0.32, 0.29). Furthermore, the fluorescence emission of p-AD in THF at 0 °C also showed a near-white light emission with chromaticity coordinates (x, y) of (0.34, 0.27). Such multifunctional rotors with readily tunable emission in the red region and prominent temperature- and viscosity-sensing abilities are promising for sensing and bioimaging applications.
区域异构体给体-受体(AD)分子转子(p-AD、m-AD 和 m-ADA)被合成并进行了表征,其中偶联体 p-AD 和 m-AD 以及三联体 m-ADA 包含 4,4-二氟-4-硼-3a,4a-二氮杂-s-茚(BODIPY)和苯并二噻吩(BDT)作为电子受体和电子给体。在所有化合物中,供体和受体部分通过苯基间隔基电子解耦,通过对位偶联或间位偶联。偶联体 p-AD 和 m-AD 表现出明显不同的光物理特性,其中偶联体 p-AD 在约 654nm 处显示出 TICT 带,其斯托克斯位移约为 150nm,表现出明显的溶剂变色性。然而,间位区域异构体三联体 m-ADA 在溶液中表现出良好的聚集。值得注意的是,由于温度可调谐和溶剂粘度依赖性发射,所有化合物都表现出高效的比率温度传感,具有正和负温度系数以及粘度传感。有趣的是,偶联体 m-AD(在 10/90v/vTHF/水中)的荧光显示出近白光发射,CIE 色度坐标(x,y)为(0.32,0.29)。此外,在 THF 中 0°C 下的 p-AD 的荧光发射也显示出近白光发射,CIE 色度坐标(x,y)为(0.34,0.27)。这些多功能转子在红色区域具有易于调节的发射,以及显著的温度和粘度传感能力,有望应用于传感和生物成像。