Bio-inspired charge photoaccumulation: from the design of novel systems to multielectronic redox process optimization

光合作用是设计用于转换和储存太阳能的创新分子装置的迷人灵感来源。然而，感兴趣的应用依赖于多电子催化过程，而光驱动过程本质上是单电子事件。由于特殊的辅因子，大自然完美地控制了这种明显的不匹配，能够通过将这些过程与质子转移结合起来，一次积累并传递两个电子。因此，PhotoAcc旨在通过从这些生物辅助因子，特别是黄素中获得灵感，开发新的电荷光积累系统。该项目将受益于四个国际公认的研究小组的互补专业知识：(i)在（TD） dft预测方法的支持下进行合成，以允许定制光电特性；（ii）通过各种电化学和光谱表征来破译其电子特性，包括先进的EPR技术来识别电子存储位置。（iii）评估它们在光驱动多电子/多质子氧化还原过程中的活性。

Photosynthesis is a fascinating source of inspiration to design innovative molecular devices for the conversion and storage of solar energy. Applications of interest however rely on multielectronic catalytic processes whereas light-driven processes are single-electron events in essence. Nature perfectly masters this apparent mismatch thanks to specific cofactors, able to accumulate and then to relay two electrons at a time by coupling these processes with proton transfers. PhotoAcc thus aims at developing novel charge photoaccumulation systems, by taking inspiration from such biological cofactors, flavins in particular. The project will benefit from the complementary expertise of the four internationally recognized research groups to (i) undertake their synthesis supported by a (TD)DFT-predictive approach to allow tailormade optoelectronic properties, (ii) to decipher their electronic properties by virtue of various electrochemical and spectroscopic characterizations, including advanced EPR techniques to identify the electron storage sites, and (iii) to assess their activity in light-driven multielectron/multiproton redox processes.