Boron-, carbon-, and silicon-bridged 1,12-dihydroxy-perylene bisimides with tuned structural and optical properties

Additional data to report https://doi.org/10.1039/D3QO01389H Establishing suitable design strategies to tailor the functional properties of perylene bisimide (PBI) dyes are critical for their successful application in various devices. Herein, we report a new synthetic strategy to tune their structural and fluorescence properties by employing 1,12-bay-substitution pattern that has been seldomly investigated in the past. Central to the strategy is the use of 1,12-dihydroxy-PBI as a starting compound and the subsequent bridging of these hydroxy bay-functional groups with either a boron, carbon or silicon atom resulting in derivatives with rigidified perylene core. This is followed by a detailed exploration of synthetic possibilities to functionalize the unsubstituted 6,7-positions at the opposite bay area to achieve novel perylene dyes with excellent structural and optical properties. The fluorescence color could be tuned from green to dark-orange while retaining the almost unity fluorescence quantum yield in solution. Moreover, a strong fluorescence with quantum yields as high as 40% has been observed for powders, which clearly illustrates the potential of the presented structural design to obtain new solid-state emitters.补充数据详见：https://doi.org/10.1039/D3QO01389H。开发适配性设计策略以调控苝二酰亚胺（perylene bisimide, PBI）染料的功能特性，对其在各类器件中的成功应用至关重要。本研究提出一种全新合成策略，通过采用过往鲜有探究的1,12-湾位取代模式，调控苝二酰亚胺的结构与荧光性能。该策略的核心是以1,12-二羟基苝二酰亚胺为起始原料，通过硼、碳或硅原子桥连这些湾位羟基官能团，得到苝核刚性化的衍生物。后续我们系统探究了在另一侧湾区未取代的6,7位进行官能化的合成路径，以获得兼具优异结构与光学性能的新型苝系染料。该类染料在溶液中的荧光颜色可从绿色调控至深橙色，同时保持近乎100%的荧光量子产率。此外，其粉体材料仍可展现出高达40%量子产率的强荧光，这充分证明了本研究提出的结构设计策略在开发新型固态发光材料方面的应用潜力。