Photo-redox reactivity of titanium-oxo clusters: Mechanistic insight into a two-electron intramolecular process, and structural characterisation of mixed-valent Ti(iii)/Ti(iv) products

Tobias Krämer, Floriana Tuna, Sebastian D. Pike*

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    Abstract

    Small titanium-oxo-alkoxide clusters, [TiO(OR)(O2PR′2)]4, synthesised by the stoichiometric reaction of Ti(OiPr)4, phosphinic acid and water, undergo a photo-redox transformation under long-wave UV light. The photo-reaction generates blue coloured, mixed-valence Ti(iii)/Ti(iv)-oxo clusters alongside acetone and isopropanol by-products. This reactivity indicates the ability for photoactivated charge separation to occur in even the smallest of Ti-oxo clusters. EPR and NMR spectroscopic studies support a photo-redox mechanism that occurs via an intramolecular, two-electron pathway, directly relating to current doubling effects observed at TiO2 photoanodes in the presence of alcohols. The rate of photo-reaction is solvent dependent, with donor solvents supporting the formation of low coordinate Ti(iii) sites. The nature of the electronic transition is identified by DFT and TDDFT calculations as an oxygen to titanium charge transfer and it is possible to finetune the UV absorption onset observed by changing the phosphinate ligand. A two-electron photo-reduced cluster, [Ti4O4(O2PPh2)6], forms spontaneously from the photo-reaction and its structure is identified by X-ray crystallography with supporting DFT calculations. These indicate that [Ti4O4(O2PPh2)6] is high-spin and contains two ferromagnetically coupled electrons delocalised over the Ti4 core. [Ti4O4(O2PPh2)6] undergoes rapid oxidation in air in the solid-state and performs a remarkable single-crystal to single-crystal transformation, to form a stable cluster-superoxide salt.

    Original languageEnglish
    Pages (from-to)6886-6898
    Number of pages13
    JournalChemical Science
    Volume10
    Issue number28
    Early online date7 Jun 2019
    DOIs
    Publication statusPublished - 2019

    Research Beacons, Institutes and Platforms

    • Photon Science Institute

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