Article Dans Une Revue Inorganic Chemistry Année : 2026

Supramolecular Control of Photoinduced Electron Transfer between Tungsten Halide Clusters and Polyoxometalates in Water

Emmanuel Cadot

Résumé

Identifying systems composed of earth-abundant elements capable of photoinduced electron-transfer represents a major breakthrough for the development of sustainable photocatalytic processes. Herein, we demonstrate that octahedral tungsten-halide clusters constitute a promising new class of robust photosensitizers, owing to their exceptional chemical stability, intense luminescence, and long-lived triplet excited states. Upon irradiation in aqueous solution, these species transfer an electron to polyoxometalates (POMs), well-known molecular catalysts capable of multielectron redox chemistry. More specifically, we investigate the photophysical properties of supramolecular systems combining the cluster-based motif [{W6Ii8}Cla6]2- and a series of archetypal POMs ([PW12O40]3-, [SiW12O40]4-, [BW12O40]5-, [P2W18O62]6-) as electron-acceptor units, in the presence of γ-cyclodextrin (γ-CD), which acts as both a supramolecular assembly scaffold and a stabilizing agent. The photoinduced electron-transfer process was investigated using steady-state and time-resolved optical spectroscopy, complemented by spectro-electrochemical measurements, which unambiguously confirm electron transfer from the excited cluster to the POMs. Furthermore, we demonstrate that both the ionic charge of the POMs and the presence of γ-CD significantly influence the efficiency of the process. This work highlights the dual role of γ-CD, which facilitates the association of two negatively charged inorganic units and stabilizes the charge-separated state by maintaining an appropriate spatial arrangement within the supramolecular assembly.

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hal-05561861 , version 1 (21-03-2026)

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Thi Huyen My Dang, Anam Fatima, Maxime Lajoye, Clément Falaise, Emmanuel Cadot, et al.. Supramolecular Control of Photoinduced Electron Transfer between Tungsten Halide Clusters and Polyoxometalates in Water. Inorganic Chemistry, 2026, 65 (11), pp.6155-6164. ⟨10.1021/acs.inorgchem.6c00083⟩. ⟨hal-05561861⟩
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