A Fully Substituted 3-Silolene Functions as Promising Building Block for Hyperbranched Poly(Silylenevinylene)

• Published in: Macromolecular rapid communications. 2012-06, Vol.33 (12), p.1074-1079
• Main Authors: Zhao, Zujin, Guo, Yanju, Jiang, Tao, Chang, Zhengfeng, Lam, Jacky W. Y., Xu, Liwen, Qiu, Huayu, Tang, Ben Zhong
• Format: Article
• Language: English
• Subjects: 3-silolene; Applied sciences; Catalysis; Crystallography, X-Ray; Exact sciences and technology; explosive detection; fluorescence; heteroatom-containing polymers; Inorganic and organomineral polymers; Molecular Weight; Organosilicon Compounds - chemical synthesis; Organosilicon Compounds - chemistry; Physicochemistry of polymers; Polymers - chemical synthesis; Polymers - chemistry; Preparation; Silanes - chemistry; silole; X-Ray Diffraction
• ISSN: 1022-1336; 1521-3927
• DOI: 10.1002/marc.201200085

A 3‐silolene derivative, 2,2,5,5‐tetrakis(dimethylsilyl)‐1,1‐dimethyl‐3,4‐diphenyl‐3‐silolene (TDMSHS), is first synthesized and characterized by X‐ray diffraction crystallography and spectroscopic methods. Hydrosilylation polymerization of TDMSHS with 1,1‐dimethyl‐2,5‐bis(4‐ethynylphenyl)‐3,4‐diphenylsilole in the presence of Karstedt's catalyst generates a stereoregular silole‐containing hyperbranched poly(silylenevinylene) (hb‐SPSV) with a high molecular weight ($\overline{M}_{\rm w}$ = 146 000, $\overline{M}_{\rm w}$/$\overline{M}_{\rm n}$ = 1.5) in high yield (≈95%). hb‐SPSV exhibits excellent thermal stability and strong fluorescence, and the emission of its aggregates in aqueous mixture can be quenched efficiently by picric acid with large quenching constants KSV up to 414400 M−1. A fully substituted 3‐silolene bearing four dimethylsilyl groups is first synthesized, whose hydrosilylation with diethynylsilole in the presence of Karstedt's catalyst generates a stereoregular silole‐containing hyperbranched poly(silylenevinylene) in high yield, with excellent thermal stability, strong fluorescence, and sensitive response to explosives.