Polysilanes on surfaces

Naito, Masanobu; Fujiki, Michiya

doi:10.1039/b710423e

Cited by 26 publications

(19 citation statements)

References 145 publications

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“…Yet increased structural complexity in polysilanes has great potential to lead to novel properties . Current efforts focus on organic side chains: hybrid σ,π‐silanes are efficient hole transport materials and undergo intramolecular photoinduced charge transfer, donor–acceptor systems display nonlinear optical behavior, and stereogenic centers or fluorinated groups control the global conformation and absorbance properties in helically chiral polysilanes …”

Section: Methodssupporting

confidence: 88%

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

et al. 2016

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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.

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Section: Methodssupporting

confidence: 88%

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

et al. 2016

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“…2 Several reviews have appeared in the past year outlining the synthesis and properties of catenated group 14 element polymers. [3][4][5][6][7][8] Particularly comprehensive is a review by Fujiki on polysilane helix generation, amplification and switching. 5 A review highlighting the eighty years of catenated germanes has appeared that covers aspects of the chemistry and properties of polygermanes.…”

Section: Books and Reviews Of Inorganic Polymer Sciencementioning

confidence: 99%

Inorganic and organometallic polymers

Gates¹

2009

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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“…Polysilanes1 have attracted considerable attention due to their usefulness as precursors for thermally stable ceramics2, 3 or materials for microlithography4, 5 and also due to their potential in the preparation of new types of materials showing semiconducting, photoconducting or nonlinear optical properties 6–8. In spite of the growing interest in polysilanes,9, 10 their methods of preparation are still limited.…”

Section: Introductionmentioning

confidence: 99%

Electroreductive block copolymerization of dichlorosilanes in the presence of disilane additives

Ishifune

Sana

Ando

et al. 2011

Polymer International

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The electroreductive polymerization of dichloromethylphenylsilane in the presence of triphenylsilyl group-containing disilanes such as hexaphenyldisilane followed by the electroreductive termination with chlorotriphenylsilane afforded triphenylsilyl group-terminated polymethylphenylsilane in 15-32% yield. The isolated polymethylphenylsilane (M n = 3350 g mol −1 , M w /M n = 1.4) was found to react as a macroinitiator to copolymerize with dibutyldichlorosilane under electroreductive conditions producing the corresponding block copolymer (M n = 4730 g mol −1 , M w /M n = 1.2) in 38% yield. The ratio of monomer units (-MeSiPh-to-BuSiBu-) of the copolymer was determined to be 75 : 25 using 1 H NMR analysis, which was in good agreement with the calculated ratio (74 : 26) on the assumption that molecular weight of the macroinitiator was not changed. The block structure of the resulting copolymer, poly(methylphenylsilane)-block-poly(dibutylsilane), was also confirmed by comparing its 1 H NMR and UV absorption spectra with those of polymethylphenylsilane, polydibutylsilane and a statistical copolymer prepared by electroreductive polymerization of dichloromethylphenylsilane with dibutyldichlorosilane. This method is applicable to the preparation of other types of macroinitiator such as triphenylsilyl group-terminated polydibutylsilane, and polydibutylsilane-block-polymethylphenylsilane was also obtained using this macroinitiator.

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Polysilanes on surfaces

Cited by 26 publications

References 145 publications

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

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

Inorganic and organometallic polymers

Electroreductive block copolymerization of dichlorosilanes in the presence of disilane additives

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