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

建议开发分子系统，该分子系统允许在外部触发器(开关)的控制下诱导富电子的P-P键的激活，并由此建立用于产生化学活性自由基的特定机制，其可能的应用例如聚合引发剂、阻燃剂或长期用于太阳能电池。为此，计划制备氨基取代的双膦和低聚膦，它们将反应性单键骨架与二茂铁单元结合在一起，在明确的分子环境中作为光化学和氧化还原有源天线和分子内信号发射器。对它们的反应性的研究将集中在阐明通过化学、电化学或光化学诱导二茂铁部分的氧化和连续的分子内电子转移来产生磷酰基自由基的途径，这些自由基的简明光谱表征，以及它们的后续反应。这些实验工作与详细的计算研究相结合，预计将提供对正在进行的过程的概念性理解，有望表征前所未有的电子结构，并学习控制和微调观察到的反应性，作为长期开发定制应用的基础。

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.