Polymeric organosilicon systems. XXIX. Thermal properties of poly[(disilanylene)oligophenylenes]

Ohshita, Joji; Sugimoto, Kazunori; Watanabe, T.; Kunai, Atsutaka; Ishikawa, Mitsuo; Aoyama, Susumu

doi:10.1016/s0022-328x(98)00702-5

Cited by 10 publications

(6 citation statements)

References 17 publications

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“…The characterization data are consistent with that reported in the literature 21 . The characterization data are consistent with that reported in the literature 26 . The characterization data are consistent with that reported in the literature 27 .…”

Section: S67supporting

confidence: 91%

“…Notably, the catalyst was stable during the 300-h reaction without any noticeable structural change (Supplementary Figs. [24][25][26][27], affording a total turnover number (TON) of 130000 on the basis of the total amount of Co.…”

mentioning

confidence: 99%

“…4B). These motifs are valuable precursors for borosilicate materials, heat-and chemical-resistant polymers, and polymer sensors [24][25][26] .…”

mentioning

confidence: 99%

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Nitrogen-neighboured single cobalt sites enable heterogeneous oxidase-type catalysis

Cao

Zhang²,

Peng

et al. 2022

Preprint

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Development of biomimetic catalytic systems that can imitate or even surpass natural enzymes remains an ongoing challenge 1–3. This is particularly true in the context of accessing non-natural reactions by bioinspired approaches, which offer intriguing possibilities for benign and affordable chemical synthesis 4. Exploiting the untapped potential of inorganic solids by translating complex knowledge in (bio)molecular-based systems may constitute a potentially useful strategy for such purpose 5, but efforts to capitalize on the minimum catalytic unit of a versatile solid matrix have been largely unsuccessful. Here, we show how an all-inorganic biomimetic system bearing robust nitrogen-neighboured single cobalt site/pyridinic-N site (Co-N4/Py-N) pairs can act cooperatively as an oxidase mimic, which renders an engaged coupling of oxygen (O2) reduction with synthetically beneficial chemical transformations. By developing this broadly applicable platform, the scalable synthesis of greater than 100 industrially and pharmaceutically appealing O-silylated compounds via the unprecedented aerobic oxidation of hydrosilane under ambient conditions is demonstrated. Moreover, this heterogeneous oxidase mimic also offers potential for expanding the catalytic scope of enzymatic synthesis. We anticipate that the strategy demonstrated here will pave a new avenue for understanding the underlying nature of redox enzymes and open up a new class of material systems for artificial biomimetics.

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Section: S67supporting

confidence: 91%

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confidence: 99%

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Nitrogen-neighboured single cobalt sites enable heterogeneous oxidase-type catalysis

Cao

Zhang²,

Peng

et al. 2022

Preprint

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“…Polymers possessing an alternating arrangement of a π‐conjugated unit 83 such as phenylene, 84 ethenylene, 85–87 and a sil(an)ylene unit in the backbone were synthesized by coupling reactions, 86,88 thermal cyclopolymerization 89,90 and a variety of ring‐opening polymerization (ROP) reactions including anionic, 91–95 thermolytic, and catalytic coordination techniques, 96 each with some limitations.…”

Section: Preceramic Polymer Synthesismentioning

confidence: 99%

Polymer‐Derived Ceramics: 40 Years of Research and Innovation in Advanced Ceramics

Colombo

Mera

Riedel

et al. 2010

Journal of the American Ceramic Society

1,068

582

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Preceramic polymers were proposed over 30 years ago as precursors for the fabrication of mainly Si-based advanced ceramics, generally denoted as polymer-derived ceramics (PDCs). The polymer to ceramic transformation process enabled significant technological breakthroughs in ceramic science and technology, such as the development of ceramic fibers, coatings, or ceramics stable at ultrahigh temperatures (up to 20001C) with respect to decomposition, crystallization, phase separation, and creep. In recent years, several important advances have been achieved such as the discovery of a variety of functional properties associated with PDCs. Moreover, novel insights into their structure at the nanoscale level have contributed to the fundamental understanding of the various useful and unique features of PDCs related to their high chemical durability or high creep resistance or semiconducting behavior. From the processing point of view, preceramic polymers have been used as reactive binders to produce technical ceramics, they have been manipulated to allow for the formation of ordered pores in the meso-range, they have been tested for joining advanced ceramic components, and have been processed into bulk or macroporous components. Consequently, possible fields of applications of PDCs have been extended significantly by the recent research and development activities. Several key engineering fields suitable for application of PDCs include high-temperature-resistant materials (energy materials, automotive, aerospace, etc.), hard materials, chemical engineering (catalyst support, food- and biotechnology, etc.), or functional materials in electrical engineering as well as in micro/ nanoelectronics. The science and technological development of PDCs are highly interdisciplinary, at the forefront of micro- and nanoscience and technology, with expertise provided by chemists, physicists, mineralogists, and materials scientists, and engineers. Moreover, several specialized industries have already commercialized components based on PDCs, and the production and availability of the precursors used has dramatically increased over the past few years. In this feature article, we highlight the following scientific issues related to advanced PDCs research: (1) General synthesis procedures to produce silicon-based preceramic polymers. (2) Special microstructural features of PDCs. (3) Unusual materials properties of PDCs, that are related to their unique nanosized microstructure that makes preceramic polymers of great and topical interest to researchers across a wide spectrum of disciplines. (4) Processing strategies to fabricate ceramic components from preceramic polymers. (5) Discussion and presentation of several examples of possible real-life applications that take advantage of the special characteristics of preceramic polymers. Note: In the past, a wide range of specialized international symposia have been devoted to PDCs, in particular organized by the American Ceramic Society, the European Materials Society, and the Materials Research S...

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“…Recently, much attention has been focused on organosilicone compounds with an alternating arrangement of an SiSi bond and a π‐electron system such as ethenylene,1 ethynylene,2 diethynylene,3 furylene,4 thienylene,5, 6 and phenylene7, 8 in the polymer backbones because of their sensitivity to radiation and intriguing semiconducting properties with doping. For example, the poly[(disilanylene)phenylenes] are insulators; on treatment of the polymers with antimony pentafluoride vapor they become conducting 8…”

Section: Introductionmentioning

confidence: 99%

Synthesis and optical and thermal properties of poly[methyl(2,9‐diphenyl‐ 7,8‐benzophenanthryl)silylene‐co‐1,4‐bis(methylphenylsilyl)phenylene]

Li¹,

Qiu²,

Jiang³

et al. 2006

Polymer International

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Poly[methyl(2,9‐diphenyl‐7,8‐benzophenanthryl)silylene‐co‐1,4‐bis(methylphenylsilyl)phenylene] (PMBS‐co‐BSP) was synthesized by the condensation reaction of dichloromethyl(2,9‐diphenyl‐7,8‐benzophenanthryl)silane and 1,4‐bis(chloromethylphenylsilyl)benzene with sodium in toluene. Optical and thermal behavior of the polymer was investigated. Because of the introduction of substituted benzophenanthryl groups into the Si atoms of the polymer, the UV absorption wavelength of the PMBS‐co‐BSP red‐shifted significantly in the UV region, and a strong photoluminescence band was observed in the visible region other than the near‐UV photoluminescence typical of normal polysilane. The photochemical behavior was examined both in solution and in thin film by fluorescence and UV spectroscopy. Irradiation of the PMBS‐co‐BSP with a low‐pressure mercury lamp in solution resulted in homolytic scission of silicone–silicone bonds; the fluorescence emission intensities decreased gradually with increasing UV irradiation time and the maximum emission wavelength blue‐shifted significantly. Irradiation of thin solid films of the PMBS‐co‐BSP in air led to the formation of photoproducts containing SiOH and SiOSi groups. The PMBS‐co‐BSP began to weigh less at about 300 °C and the weight loss of the polymer at 700 °C was calculated to be 75% of the initial weight in N2. Copyright © 2006 Society of Chemical Industry

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Polymeric organosilicon systems. XXIX. Thermal properties of poly[(disilanylene)oligophenylenes]

Cited by 10 publications

References 17 publications

Nitrogen-neighboured single cobalt sites enable heterogeneous oxidase-type catalysis

Nitrogen-neighboured single cobalt sites enable heterogeneous oxidase-type catalysis

Polymer‐Derived Ceramics: 40 Years of Research and Innovation in Advanced Ceramics

Synthesis and optical and thermal properties of poly[methyl(2,9‐diphenyl‐ 7,8‐benzophenanthryl)silylene‐co‐1,4‐bis(methylphenylsilyl)phenylene]

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