The Role of the Lowest Excited Triplet State in Defining the Rate of Photoaquation of Hexacyanometalates

Photosolvation is a type of ligand substitution reaction started by irradiation of a solution with light, triggering the replacement of a ligand with a molecule from the solvent. The excited state is created through many possible pathways. For the class of hexacyanides of groups 8 and 9 of the perio...

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Published in:The journal of physical chemistry letters 2024-01, Vol.15 (1), p.241-247
Main Authors: Mascarenhas, Eric J., Fondell, Mattis, Büchner, Robby, Eckert, Sebastian, Vaz da Cruz, Vinicius, Föhlisch, Alexander
Format: Article
Language:English
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Physical Insights into Chemistry, Catalysis, and Interfaces
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Summary:Photosolvation is a type of ligand substitution reaction started by irradiation of a solution with light, triggering the replacement of a ligand with a molecule from the solvent. The excited state is created through many possible pathways. For the class of hexacyanides of groups 8 and 9 of the periodic table, irradiation in the ligand field band is followed by intersystem crossing to the lowest excited triplet state, which we propose to mediate the photoaquation reaction in this class of complexes. In this study, we present time-resolved X-ray absorption data showing indications of the triplet intermediate state in the cobalt­(III) hexacyanide complex and we discuss general aspects of the photoaquation reaction in comparison with reported data on the isoelectronic iron­(II) hexacyanide. Quantum chemical calculations are analyzed and suggest that the nature of the lowest excited triplet state in each complex can explain the drastically different rate of reactions observed.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.3c02775