Developing molecular photocatalysts that can accumulate redox equivalents as a response to photoexcitation is of great interest in order to efficiently facilitate photon-driven reactions that require multiple electrons, such as water splitting and CO<sub>2</sub> reduction. Revealing and understanding fundamental excited state charge accumulation pathways in chromophore-catalyst supramolecular assemblies is key to achieve and control charge accumulation in these systems. A series of Cu(I) HETPHEN anthraquinone supramolecular assemblies were synthesized as model complexes to probe the charge accumulation pathways under illumination. The assemblies were designed and consist of Cu(I) HETPHEN motifs, acting as light absorbers and electron donors, and an anthraquinone central moiety, functioning as an electron acceptor and charge accumulation site. The structural characterization was achieved by NMR and X-ray crystallography and the steady state optical and electrochemical properties were investigated by UV/vis and cyclovoltammetry. Optical spectroelectrochemical studies were employed to capture the singly and doubly reduced anthraquinone species, which were corroborated by DFT calculation. The photoinduced charge accumulation of these complexes were investigated with chemical reductant. The photoexcited state dynamics has been investigated by optical transient absorption and time-resolved infrared spectroscopy.

Building a Cu(I) HETPHEN anthraquinone supramolecular assembly for investigating key charge accumulation pathways in solar energy conversion

ACS Fall 2021

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