Structurally stabilized polystannanes

导电聚合物传统上构建在有机框架上，并且通常需要氧化或还原掺杂以有效地导电。这些导电有机塑料依赖于离域π网络和小的带隙来传输电子。与碳基本征导电聚合物不同，具有硅、锗或锡原子主链的无机均聚物利用σ离域来导电。 在这些第14族元素中，锡的均聚物最好地模仿其元素形式，并在其自然状态下显示出半导体性质，并且当掺杂时可以制成高导电性。用这些材料制造器件或制备一维导电聚合物线的前景受到其极端光和湿度敏感性的阻碍。 在该提议中，将具有光吸收侧基的更高配位锡物质（配位键合的5-或6-配位锡）并入的新策略应该提供提供光和水分稳定的聚锡烷的最佳机会。通过与氧或氮原子的配价相互作用在锡处的更高配位数通过阻断进入配位位点有效地保护敏感的Sn-Sn键免受亲核攻击。此外，用于捕获光子的UVA（紫外吸收小分子）基团的存在降低了均聚物中光致断裂的可能性。设计了一系列新的二氢化锡单体，并进行了脱氢偶联聚合反应。 与常规聚锡烷相比，这些新聚合物在稳定性和导电性能方面应显示出显著差异。所有这些调查的中心将是本科生和研究生在制备和表征主族无机聚合物的技能和技术方面的培训。 这项工作提出了显着扩大知识和实用性的第14族聚合物，特别是聚锡烷。 它将导致无机化学和无机聚合物的进步，并提供最好的机会，使导电聚合物线与锡。

Conductive polymers have traditionally been built on organic frameworks and often require oxidative or reductive doping to effectively conduct electricity. These conductive organic plastics rely on a delocalized pi network and small band gaps in order to transport electrons. Unlike carbon based intrinsically conducting polymers, inorganic homopolymers with backbones of silicon, germanium or tin atoms utilize sigma delocalization to be conductive. Of these Group 14 elements, the homopolymers of tin best emulate its elemental form and display semi-conducting properties in its natural state and can be made highly conducting when doped. The promise of fabricating devices or preparing one-dimensional conductive polymeric wires with these materials has been hampered by their extreme light and moisture sensitivity. In this proposal, a new strategy to incorporate higher coordinate tin species (datively bonded 5- or 6-coordinate tin) with light absorbing side groups should provide the best opportunity to deliver light and moisture stable polystannanes. Higher coordination numbers at tin through dative interactions with oxygen or nitrogen atoms effectively protects the sensitive Sn-Sn bonds from nucleophilic attack by blocking access to a coordination site. Additionally, the presence of a UVA (ultra-violet absorbing small molecule) group to capture photons reduces the likelihood of photoscission in the homopolymers. The design of a series of new tin dihydride monomers and subsequent polymerization by dehydrocoupling will be undertaken. These new polymers should display dramatic differences in stability and conduction properties compared to regular polystannanes. Central to all these investigations will be the training of undergraduate and graduate students in the skills and techniques of preparing and characterizing main group inorganic polymers. This work proposes to dramatically expand the knowledge and usefulness of Group 14 polymers, in particular, polystannanes. It will lead to advances in both inorganic chemistry and inorganic polymers, and provide the best opportunity to make conductive polymeric wires with tin.