Sigma delocalisation via Group 13 Homocatenation

通过 Group 13 Homocatenation 进行 Sigma 离域

• 批准号: EP/E05921X/1
• 负责人: Michael Hill
• 金额: $ 41.53万
• 依托单位: University of Bath
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2007
• 资助国家: 英国
• 起止时间: 2007 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FE05921X%2F1
• 关键词: Sigma; delocalisation; via; Group; 13

Organic polymers have many well-established uses in everyday life. Plastics, elastomers, films and fibres are used in areas as diverse as clothing, car tyres, compact discs, packaging materials and prostheses. By contrast the chemistry of polymers featuring inorganic elements is generally at a much more primitive state of development due a paucity of suitable synthetic routes. Nevertheless, incorporation of main group or transition metals into a polymer main chain can lead to interesting and useful properties, such as low temperature flexibility, high thermal and oxidative stability and intriguing electrical and optical characteristics arising from unusual electronic effects such as delocalisation of sigma-electrons. This proposal seeks to build upon our recent report in Science that group 13 centres, when linked in extended linear chains, display delocalised electronic properties. Similar properties are currently the preserve of pi-conjugated 'plastic electronic' materials such as polythiophene and polyacetylene which are of interest in a wide array of possible applications, from solar cells and light emitting devices to molecular computing . In the case of our target molecules the electroactivity is a result of delocalisation of the electrons along the sigma backbone of the polymeric unit. We shall devise new routes to a variety of polymeric systems based upon all the elements of group 13 (excepting thallium) and will test our hypothesis that the electronic band gaps will be largely dependent upon the identity of the constituent group 13 element both experimentally and theoretically.

有机聚合物在日常生活中有许多公认的用途。塑料、弹性体、薄膜和纤维广泛应用于服装、汽车轮胎、光盘、包装材料和假肢等领域。相比之下，由于缺乏合适的合成途径，以无机元素为特征的聚合物化学通常处于更原始的发展状态。然而，在聚合物主链中加入主基团或过渡金属可以产生有趣和有用的特性，例如低温柔韧性，高热稳定性和氧化稳定性，以及由不寻常的电子效应（如西格玛电子的离域）引起的有趣的电学和光学特性。这个提议试图建立在我们最近在《科学》杂志上的报告的基础上，该报告指出，当以延伸的线性链连接时，13个中心显示出离域电子特性。类似的性质目前是π共轭“塑料电子”材料的保留，如聚噻吩和聚乙炔，它们在从太阳能电池和发光器件到分子计算的广泛应用中都很有意义。在我们的目标分子的情况下，电活性是电子沿着聚合单元的sigma主链离域的结果。我们将设计基于13族所有元素（铊除外）的各种聚合物体系的新路线，并将从实验和理论上验证我们的假设，即电子带隙将在很大程度上取决于组成13族元素的身份。

项目成果

Organoiron compounds derived from the indium 'carbene analogues', [In(N(Ar)C(Me))2CH] (Ar = dipp = 2,6-iPr2C6H3; = Mes = 2,4,6-Me3C6H2).

• DOI: 10.1039/b801160e
• 发表时间: 2008-05
• 期刊: Dalton transactions
• 影响因子: 4
• 作者: M. Hill;P. Hitchcock;R. Pongtavornpinyo

Edited by Simon Aldridge and Anthony J. Downs The Group 13 Metals Aluminium, Gallium, Indium and Thallium: Chemical Patterns and Peculiarities John Wiley & Sons, Ltd., 2011, 726 pages (hardcover) 978-0-470-68191-6

由 Simon Aldridge 和 Anthony J. Downs 编辑 第 13 族金属铝、镓、铟和铊：化学模式和特性 John Wiley

• DOI: 10.1002/aoc.1840
• 发表时间: 2011
• 期刊: Applied Organometallic Chemistry
• 影响因子: 3.9
• 作者: Hill M