Conjugated Hybrid Organosilicon Polymers from Low-Valent Silicon Precursors

来自低价硅前体的共轭杂化有机硅聚合物

• 批准号: 248841933
• 负责人: Professor Dr. David Scheschkewitz
• 金额: --
• 依托单位: Department of Chemistry
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/248841933?language=en
• 关键词: Conjugated; Hybrid; Organosilicon; Polymers; Low

We propose to synthesize conjugated silicon-containing hybrid polymers on the basis of the co-polymerization of difunctional low-valent silicon precursors with various - likewise difunctional - conjugated organic linking units.Despite various potential applications (e.g. as organic semiconductors and photoresists), the lack of versatile, high-yielding (atom-economic) and selective synthetic methods has limited the development of conjugated silicon-based polymers severely. The use of catalyst-free milder reaction conditions for polymer synthesis, as is evidenced in our preliminary results, will allow for a highly modular approach to such polymers. Byproduct-free protocols using stable difunctional low-valent silicon precursors will give rise to unprecedented yields and selectivities. Three different general types of polymers will be accessed: (A) polymers with alternating disilanylene and phenylene-type repeat units, (B) polymers with novel homo/hetero-cyclic silane motifs as repeat units that incorporate exocyclic unsaturated silicon moieties, and (C) polymers with cross-conjugated unsaturated silicon bonds. In the cases of (B) and (C) facile post-polymerization functionalization via the highly reactive Si=C and Si=Si units is anticipated.A variety of silicon-based repeat units (disilacyclobutene, silaaziridine, aza/phosphasilirene, cyclotrisilane, trisilacyclopentadiene) will thus be employed in the polymer backbone in alternating fashion with pi-conjugated organic linkers. The various conjugative pathways at our disposal (e.g. sigma-pi overlap, Walsh orbitals, cross-hyperconjugation etc.) will undoubtedly influence the optoelectronic and mechanical properties of the materials. The modularity of our concept with regards to both the organic and the unsaturated silicon co-monomers will furnish valuable data for the deduction of structure-property relationships in all of primary, secondary and (ultimately) tertiary structure of the polymers.

我们建议在双官能低价硅前驱体与各种类似双官能的共轭有机连接单元共聚合的基础上合成共轭含硅杂化聚合物。尽管有各种潜在的应用（如有机半导体和光抗蚀剂），但缺乏通用的、高产的（原子经济的）和选择性的合成方法严重限制了共轭硅基聚合物的发展。使用无催化剂的温和反应条件进行聚合物合成，正如我们的初步结果所证明的那样，将允许高度模块化的方法来合成这种聚合物。使用稳定的双官能低价硅前体的无副产物方案将产生前所未有的产量和选择性。三种不同类型的聚合物将被访问：(A)具有交替的二苯乙烯和苯乙烯型重复单元的聚合物，(B)具有新型的homo/杂环硅烷基序作为包含外环不饱和硅部分的重复单元的聚合物，以及(C)具有交叉共轭不饱和硅键的聚合物。在(B)和(C)的情况下，通过高度反应的Si=C和Si=Si单元，预计聚合后容易官能化。因此，各种硅基重复单元（二硅环丁烯、硅氮吡啶、氮杂/磷硅烯、环三硅烷、三硅环戊二烯）将以与偶联有机连接剂交替的方式应用于聚合物骨架中。我们所掌握的各种共轭途径（例如sigma-pi重叠、Walsh轨道、交叉超共轭等）无疑会影响材料的光电和机械性能。我们关于有机和不饱和硅共单体的概念的模块化将为推导聚合物的所有一级、二级和（最终）三级结构的结构-性质关系提供有价值的数据。

项目成果

The Addition of a Cyclopropyl Alkyne to an Asymmetrically-Substituted Disilene: A Mechanistic Study

环丙基炔与不对称取代二硅烯的加成：机理研究

• DOI: 10.1021/acs.organomet.9b00054
• 发表时间: 2019
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: A. T. Henry;J. L. Bourque;I. Vacirca;D. Scheschkewitz;K. Baines
• 通讯作者: K. Baines

Phenylene-bridged cross-conjugated 1,2,3-trisilacyclopentadienes.

亚苯基桥交联共轭 1,2,3-三硅杂环戊二烯

• DOI: 10.1039/c8cc03297a
• 发表时间: 2018
• 期刊: Chemical communications
• 影响因子: 4.9
• 作者: H. Zhao;L. Klemmer;M. J. Cowley;M. Majumdar;V. Huch;M. Zimmer;D. Scheschkewitz
• 通讯作者: D. Scheschkewitz