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UV/VIS spectroscopy of Copper Formate Clusters: Insight into Metal-Ligand Photochemistry.

08:00 EDT 10th March 2020 | BioPortfolio

Summary of "UV/VIS spectroscopy of Copper Formate Clusters: Insight into Metal-Ligand Photochemistry."

The electronic structure and the photochemistry of copper formate clusters Cu(I)2(HCO2)3- and Cu(II)n(HCO2)2n+1-, n ≤ 8, are investigated in the gas phase using UV/Vis spectroscopy in combination with quantum chemical calculations. A clear difference in the spectra of clusters with Cu(I) and Cu(II) copper ions is observed. For the Cu(I) species, transitions between copper d and s/p orbitals are recorded. For stoichiometric Cu(II) formate clusters, the spectra are dominated by copper d-d transitions and charge transfer excitations from formate to the vacant copper d orbital. Calculations reveal the existence of several energetically low-lying isomers, and the energetic position of the electronic transitions depends strongly on the specific isomer. The oxidation state of the copper centers governs the photochemistry. In Cu(II)(HCO2)3-, fast internal conversion into the electronic ground state is observed, leading to statistical dissociation; for charge transfer excitations, specific excited state reaction channels are observed in addition, like formyl radical loss. In Cu(I)2(HCO2)3-, the system relaxes to a local minimum on an excited state potential energy surface and might undergo fluorescence or reach a conical intersection to the ground state, in both cases providing substantial energy for statistical decomposition. Alternatively, a Cu(II)(HCO2)3Cu(0)- biradical structure is formed in the excited state, which gives rise to the photochemical loss of a neutral copper atom.

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Name: Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
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