METAL-TEMPLATED SELF-ASSEMBLY OF COBALOXIME-BASED PHOTOCATALYSTS

摘要

Natural photosynthetic systems precisely position molecular light-harvesting and catalytic modules into complex, hierarchical protein host frameworks which create directional electron transfer pathways and stabilize long-lived charge separated states.Remarkably, these complex structures are composed wholly of earth-abundant elements and structurally bound by generally weak but specific supramolecular interactions. Supramolecular assembly techniques offer mechanisms to 1) stabilize traditional small molecule electrocatalysts, 2) promote efficient photoinduced electron transfer (PET) and stabilization of charge-separated states, and 3) enable dynamic self-healing pathways. In this paper, we will describe our recent efforts to implement biological design principles to develop and discover new abiotic photocatalysts towards the goal of artificial photosynthesis. To address fundamental design questions and their impact on electron transfer and charge separation, we have developed new metal-templated photocatalysts (Figure 1) and have begun to map the structure-function landscape using ultrafast and nanosecond transient optical spectroscopy.