Two novel luminescent triarylborane polymeric Lewis acids and the corresponding molecular model compounds were prepared, studies on their photophysical properties performed, and applications as supported catalysts in Lewis acid-catalyzed hydrosilylation reactions explored. Variations of the substituents in the ortho-position of a phenylene linker between the Lewis acidic borane and the polystyrene framework lead to steric and electronic fine-tuning while retaining the high Lewis acidity of the boron center. The polymeric Lewis acids serve as effective catalysts in the hydrosilylation of aldehyde, ketone, and imine compounds and because of their distinct solubility characteristics are readily amenable to recycling. In addition, as a result of the twisted biphenyl donor−π-acceptor structure, both the styrene copolymers and model compounds display strong luminescence in solution and the solid state, encompassing prompt fluorescence and in the case of the chlorophenyl-linked derivative also longer-lived room temperature phosphorescence (RTP). Consistent with quantum-chemical calculations, the greater donor strength of the 2,6-dimethylphenyl in comparison to the 2-chlorophenyl linker leads to a red-shifted emission, while the chloro substituent leads to a larger gap between singlet and triplet excited states. In the solid state, distinctly different emission properties are observed for the polymers in comparison to the molecular compounds because of the site isolation of the chromophores embedded in the polymer matrix.

中文翻译：

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量身定制的三芳基硼烷聚合物作为载体的催化剂和发光材料

制备了两种新型的发光三芳基硼烷聚合物路易斯酸和相应的分子模型化合物，对其光物理性质进行了研究，并探讨了其在路易斯酸催化的氢化硅烷化反应中作为载体催化剂的应用。邻位取代基的变化在路易斯酸性硼烷和聚苯乙烯骨架之间的亚苯基连接基的位置导致空间和电子微调，同时保持硼中心的高路易斯酸度。聚合的路易斯酸在醛，酮和亚胺化合物的氢化硅烷化中充当有效的催化剂，并且由于其独特的溶解度特性而易于回收。另外，由于扭曲的联苯供体-π-受体结构，苯乙烯共聚物和模型化合物在溶液和固态下均显示出强发光，包括迅速的荧光，并且在氯苯基连接的衍生物的情况下，也更长-室温室温磷光（RTP）。与量子化学计算一致，2的供体强度更大 与2-氯苯基连接基相比，6-二甲基苯基导致红移发射，而氯取代基导致单线态和三线态激发态之间更大的间隙。在固态下，由于嵌入在聚合物基质中的生色团的位置隔离，与分子化合物相比，观察到聚合物的发射特性明显不同。