title: Synthesis of a Fragment of Crystalline Silicon: Poly(Cyclosilane).
abstract: 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.
authors.affiliation: Department of Chemistry, Johns Hopkins University, 3400 N. Charles St, Baltimore, MD, 21218, USA.
authors.forename: Eric M
authors.initials: EM
authors.lastname: Press
authors.affiliation: Department of Chemistry, Johns Hopkins University, 3400 N. Charles St, Baltimore, MD, 21218, USA.
authors.forename: Eric A
authors.initials: EA
authors.lastname: Marro
authors.affiliation: Department of Chemistry, University of Massachusetts, Amherst, USA.
authors.forename: Sravan K
authors.initials: SK
authors.lastname: Surampudi
authors.affiliation: Department of Chemistry, Johns Hopkins University, 3400 N. Charles St, Baltimore, MD, 21218, USA.
authors.forename: Maxime A
authors.initials: MA
authors.lastname: Siegler
authors.affiliation: Department of Chemistry, Johns Hopkins University, 3400 N. Charles St, Baltimore, MD, 21218, USA.
authors.forename: Joel A
authors.initials: JA
authors.lastname: Tang
authors.affiliation: Department of Chemistry, Johns Hopkins University, 3400 N. Charles St, Baltimore, MD, 21218, USA.
authors.forename: Rebekka S
authors.initials: RS
authors.lastname: Klausen
keywords: hybrid materials; main-group polymers; polycycles; silanes; synthesis design