UV/Vis Spectroscopy of Copper Formate Clusters: Insight into Metal-Ligand Photochemistry

Chemistry : a European Journal
Tobias F PascherMartin K Beyer

Abstract

The electronic structure and photochemistry of copper formate clusters, CuI2 (HCO2 )3- and CuIIn (HCO2 )2n+1- , n≤8, are investigated in the gas phase by using UV/Vis spectroscopy in combination with quantum chemical calculations. A clear difference in the spectra of clusters with CuI and CuII copper ions is observed. For the CuI species, transitions between copper d and s/p orbitals are recorded. For stoichiometric CuII 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 CuII (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, such as formyloxyl radical loss. In CuI2 (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...Continue Reading

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Citations

Jul 14, 2020·Theoretical Chemistry Accounts·Tobias F PascherMilan Ončák
Nov 15, 2020·The Journal of Chemical Physics·Tobias F PascherMartin K Beyer
Apr 29, 2021·Physical Chemistry Chemical Physics : PCCP·Tobias F PascherMartin K Beyer

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Methods Mentioned

BETA
infrared spectroscopy

Software Mentioned

EOM
Gaussian

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