High molecular weight poly(N-methyl-B-vinylazaborine) – a semi-inorganic B–N polystyrene analogue

Thiedemann, Birk; Gliese, Philipp J.; Hoffmann, Jonas; Lawrence, Paul G.; Sönnichsen, Frank D.; Staubitz, Anne

doi:10.1039/c6cc08599g

Cited by 61 publications

(40 citation statements)

References 42 publications

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“…This method was used even further to generate polymeric chains (Scheme ) . Examples of polymerizations of functionalized 1,2‐azaborinines by radical initiation were also reported (Scheme ). BN‐containing extended structures (mostly within fused rings) in the context of material chemistry have recently been reviewed.…”

Section: 12‐azaborininesmentioning

confidence: 99%

Recent Developments in Azaborinine Chemistry

2017

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Section: 12‐azaborininesmentioning

confidence: 99%

Recent Developments in Azaborinine Chemistry

2017

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“…[9][10][11][12] When other main group elements are introduced, the range of possibilities to lower this gap becomes larger: Strategies involve formally antiaromatic compounds such as boroles, 13 or phosphole oxides. [14][15] BN-substitution of (poly)aromatic rings [16][17] results in compounds that are formally aromatic but whose charge delocalization around the ring is severely impeded by the very polar BN-substitution, which may aide long range delocalization of electrons.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Optoelectronic Properties of Stannoles by the Judicious Choice of the Organic Substituents

et al. 2018

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1 Stannoles are organometallic rings in which the heteroatom is involved in a form of conjugation that involves excited states (σ*-π*-conjugation). Only little is known about how the substituents on the tin atom or substituents on the stannole ring determine the optoelectronic properties of these heterocycles. In this work, this has been studied experimentally and theoretically. Calculations of optimized equilibrium geometries, energy gaps between the HOMOs and LUMOs, and of the absorption spectra of a wide range of compounds were performed. The computational data showed that the substituents on the tin atom influence the optoelectronic properties to a lower extent than the substituents in the 2-and 5-positions of the ring. These substituents in the plane of the stannole ring can also have a strong influence on the overall planarity of the structure, in which mesomeric effects can play a substantial role only if the structure is planar. Thus, only structures with a planar backbone are of interest in the context of tuning optoelectronic properties. These were selected for the experimental studies. Based on this information, a series of six novel stannoles was synthesized by formation of a zirconium intermediate and subsequent transmetalation to obtain the tin compound. The calculated electronic HOMO-LUMO gaps varied between 2.94 eV and 2.68 eV.The measured absorption maxima were located between 415 nm and 448 nm as compared to theoretically calculated values ranging from 447 nm (2.77 eV) to 482 nm (2.57 eV). In addition to these optical measurements, cyclic voltammetry data could be obtained, which show two reversible oxidation processes for three of six stannoles. With this study, it could be demonstrated how the judicious choice of substituents can lead to large and predictable bathochromic shifts in the absorption spectra. ASSOCIATED CONTENT Supporting InformationThe Supporting Information is available free of charge on the ACS Publications website. It includes experimental and analytical details, NMR spectra, cyclic voltammetry and absorption spectra (PDF), crystal structure information (CIF) and all computational data (TXT).

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“…[26] BN2VN polymers are attractive candidates for investigating the proposed borapolyolefin oxidation owing to the scalable monomer synthesis. [24,25] Thesuccessful copolymerization of BN2VN and 2VN suggests the feasibility of copolymerization of styrene and BN2VN (PBN2VN-co-PS). [24,25] Thesuccessful copolymerization of BN2VN and 2VN suggests the feasibility of copolymerization of styrene and BN2VN (PBN2VN-co-PS).…”

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confidence: 99%

“…[26,32,33] We prepare BN2VN in high overall yield and in two steps from commercially available starting materials.T he multistep syntheses of monocyclic azaborine vinyl monomers limit polymerizations to the milligram scale. [24,25] Thesuccessful copolymerization of BN2VN and 2VN suggests the feasibility of copolymerization of styrene and BN2VN (PBN2VN-co-PS).…”

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A BN Aromatic Ring Strategy for Tunable Hydroxy Content in Polystyrene

et al. 2018

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BN 2-vinylnaphthalene, a BN aromatic vinyl monomer, is copolymerized with styrene under free radical conditions. Oxidation yields styrene-vinyl alcohol (SVA) statistical copolymers with tunable hydroxy group content. Comprehensive spectroscopic investigation provides proof of structure. Physical properties that vary systematically with hydroxy content include solubility and glass transition temperature. BN aromatic polymers represent a platform for the preparation of diverse functional polymeric architectures via the remarkable reaction chemistry of C-B bonds.

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High molecular weight poly(N-methyl-B-vinylazaborine) – a semi-inorganic B–N polystyrene analogue

Cited by 61 publications

References 42 publications

Recent Developments in Azaborinine Chemistry

Recent Developments in Azaborinine Chemistry

Tuning the Optoelectronic Properties of Stannoles by the Judicious Choice of the Organic Substituents

A BN Aromatic Ring Strategy for Tunable Hydroxy Content in Polystyrene

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