ERA-Chemistry Switchable activation of electron rich polyphosphorus-framework structures

ERA-Chemistry 富电子多磷骨架结构的可切换激活

• 批准号: 251655761
• 负责人: Professor Dr. Dietrich Gudat
• 金额: --
• 依托单位: Institut für Chemie
• 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 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/251655761?language=en
• 关键词: ERA; Chemistry; Switchable; activation; electron

It is proposed to develop molecular systems which allow to induce activation of an electron rich P-P bond under control of an external trigger ("switch") and to establish thereby a specific mechanism for the generation of chemically active radicals with possible application e.g. as polymerisation initiator, flame retardant or, in the long term, solar cell. To this end, it is planned to prepare amino-substituted diphosphanes and oligophosphanes which combine frameworks of reactive single bonds with ferrocene units acting as photochemically and redox active antenna and intramolecular signal transmitter in a well-defined molecular environment. Studies of their reactivity will focus on elucidating pathways to generate phosphanyl radicals by chemically, electrochemically, or photochemically induced oxidation of the ferrocene moiety and successive intramolecular electron transfer, concise spectroscopic characterisation of these radicals, and clarification of their follow-up reactions. Combination of these experimental efforts with detailed computational studies are expected to provide a conceptual understanding of the ongoing processes, with the prospect of characterizing unprecedented electronic structures and learning to control and fine tune the observed reactivities as a basis for a long-term development of tailored applications.

提出了开发允许在外部触发器（“开关”）的控制下诱导富电子P-P键的活化的分子系统，并由此建立用于产生化学活性自由基的特定机制，其具有可能的应用，例如作为聚合引发剂、阻燃剂或长期的太阳能电池。为此，计划制备氨基取代的二膦和低聚膦，其将反应性单键的联合收割机框架与在明确定义的分子环境中充当光化学和氧化还原活性天线和分子内信号传递器的二茂铁单元结合。它们的反应性的研究将集中在阐明的途径产生磷酰基自由基的化学，电化学，或光化学诱导氧化的二茂铁部分和连续的分子内电子转移，简明的光谱表征这些自由基，并澄清其后续反应。结合这些实验的努力与详细的计算研究，预计将提供一个概念上的理解正在进行的过程中，表征前所未有的电子结构和学习控制和微调所观察到的反应性作为长期发展的基础上定制的应用程序的前景。