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

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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.