Synthesis of organosilicon polymers with cyclohexasilane fragments in the main chain

Chernyavskii, A. I.; Larkin, D. Yu.; Бузин, М. И.; Chernyavskaya, N. A.

doi:10.1007/s11172-011-0049-3

Cited by 8 publications

(5 citation statements)

References 16 publications

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“…Reductive coupling of dichlorodimethylsilane yields dodecamethylcyclohexasilane (Si 6 Me 12 ) . Chlorination of Si 6 Me 12 , while yielding a mixture of structural isomers and diastereomers, is a popular route to substituted cyclohexasilanes via substitution and chromatographic separation. , Reductive heterocouplings are unselective and yield complex mixtures …”

Section: Resultsmentioning

confidence: 99%

Directional Building Blocks Determine Linear and Cyclic Silicon Architectures

et al. 2018

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Silicon nanomaterials combine earth abundance and biodegradability with exceptional electronic properties. Strategic synthesis promises access to novel architectures with well-defined surface structure, size, and shape. Herein, we describe a five-step synthesis of functional macrocyclic polysilanes. Comparison of the materials isolated from isomeric building blocks provides evidence that building block directionality controls the shape of the resulting nanomaterial. Infrared (IR) and H andSi NMR spectroscopies, coupled to computational data, provide evidence of a well-defined Si-H and Si-Me terminated structure. The intrinsic porosity and the polarization arising from the hydridic character of the Si-H bond suggest applications in lithium-ion batteries, which are supported by quantum chemical calculations.

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Section: Resultsmentioning

confidence: 99%

Directional Building Blocks Determine Linear and Cyclic Silicon Architectures

et al. 2018

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“…Dodecamethylcyclohexasilane (Si 6 Me 12 ), obtained by reductive coupling of dichlorodimethylsilane, is unselectively chlorinated, yielding a mixture of 1,3‐ and 1,4‐dichlorinated structural isomers and diastereomers . Chlorocyclosilanes have been used to prepare organometallic complexes, σ‐π hybrid materials, aminosilanes, and polymeric silicon carbide precursors . 1,4‐Functionalized cyclohexasilanes are a minor product (2 % yield) of unselective reductive coupling reactions .…”

Section: Methodsmentioning

confidence: 99%

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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“…Shimoda reported the photoinduced ring-opening polymerization of cyclopentasilane ( c -Si 5 H 10 ) to give a disperse mixture of hydrogenated polysilanes that upon pyrolysis yield amorphous silicon . Stüger , and later Chernyavskaya reported the hydrolysis and condensation of halocyclosilanes to linear and network polysiloxanes, with Chernyavskaya also reporting reductive polymerization.…”

Section: Poly(cyclosilane)s: Complex Silicon Frameworkmentioning

confidence: 99%

Conjugated Polymers Inspired by Crystalline Silicon

Marro

Klausen

2019

Chem. Mater.

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Modern technologies depend on the semiconductor silicon. Silicon nanostructures evince compelling properties including luminescence and biodegradability. Silicon-based soft matter is less explored, despite the attractive properties of conjugated polymers and small molecules inspired by crystalline silicon. This perspective describes the major synthetic approaches to polysilanes and summarizes innovations in the preparation of structurally complex functional polysilanes that combine unusual conjugation phenomena, solution processability, and morphological control. A connection is drawn between the limitations of current polymerization methodology and fine control of structure−property relationships.

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Synthesis of organosilicon polymers with cyclohexasilane fragments in the main chain

Cited by 8 publications

References 16 publications

Directional Building Blocks Determine Linear and Cyclic Silicon Architectures

Directional Building Blocks Determine Linear and Cyclic Silicon Architectures

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

Conjugated Polymers Inspired by Crystalline Silicon

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