Synthesis of a Fragment of Crystalline Silicon: Poly(Cyclosilane)

Press, Eric M.; Marro, Eric A.; Surampudi, Sravan K.; Siegler, Maxime A.; Tang, Joel A.; Klausen, Rebekka S.

doi:10.1002/anie.201610208

Synthesis of a Fragment of Crystalline Silicon: Poly(Cyclosilane)

Journal Article · Tue Nov 29 00:00:00 EST 2016 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201610208· OSTI ID:1533091

Press, Eric M. ^[1]; Marro, Eric A. ^[1]; Surampudi, Sravan K. ^[2]; Siegler, Maxime A. ^[1]; Tang, Joel A. ^[1]; Klausen, Rebekka S. ^[1]

Johns Hopkins Univ., Baltimore, MD (United States)
Univ. of Massachusetts, Amherst, MA (United States)

We report a strategic synthesis of poly(cyclosilane), a well-defined polymer inspired by crystalline silicon. The synthetic strategy relies on the design of a functionalized cyclohexasilane monomer for transition-metal-promoted dehydrocoupling polymerization. Our approach takes advantage of the dual function of the phenylsilyl group, which serves a crucial role both in the synthesis of a novel α,ω-oligosilanyl dianion and as a latent electrophile. We show that the cyclohexasilane monomer prefers a chair conformation. The monomer design ensures enhanced reactivity in transition-metal-promoted dehydrocoupling polymerization relative to secondary silanes, such as methylphenylsilane. Comprehensive NMR spectroscopy yields a detailed picture of the polymer end-group structure and microstructure. Poly(cyclosilane) has red-shifted optical absorbance relative to the monomer. We synthesize a σ–π hybrid donor–acceptor polymer by catalytic hydrosilylation.

View Accepted Manuscript (DOE)

Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0013906

OSTI ID:: 1533091

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 2 Vol. 56; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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