Gas-phase reactivity of hexanuclear molybdenum [Mo₆I₁₄]^2- and its photo-fragments towards O₂ and CO₂: combined mass spectrometry (MSⁿ) and quantum chemical simulations.

Authors

Aikaterini Tsirkou, Nina Tyminska, Richard A J O'Hair, Fabien Grasset, Yann Molard, Karine Costuas, Stéphane Cordier, Luke MacAleese

Published in

Physical chemistry chemical physics : PCCP. Oct 20, 2025. Epub Oct 20, 2025.

Abstract

The optical properties, photo-decomposition and photo-reactivity of [Mo₆I₁₄]^2- clusters and their associated photo-products are examined in the gas phase. The UV-visible optical spectrum of the electron-rich [Mo₆I₁₄]^2- cluster is measured and the wavelength dependence of the principal fragments is interpreted on the basis of the quantum chemistry (QC) simulated spectrum and detailed transitions. A special focus of attention is the photo-generated [Mo₆I₁₄]^- and photo-specific radical [Mo₆I₁₃]^2-˙ as well as halogen-depleted clusters [Mo₆I_n]^- with n < 14. The fragmentation and reaction energetics of all species are examined with a combination of mass spectrometry experiments, ion-molecule reactions with O₂ and CO₂ under irradiation and QC simulations. Reactions with O₂ are shown to be very exergonic with up to 5 eV release when O₂ is dissociated on the cluster. Experimental evidence for the photo-decomposition of CO₂ into CO and O on [Mo₆I_n]^- ions is provided together with detailed QC energetics.

PMID:
41111327
Bibliographic data and abstract were imported from PubMed on 20 Oct 2025.

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