2026-10-14T08:56:41Z https://api.figshare.com/v2/oai

oai:figshare.com:article/33908266 2026-09-17T19:00:42Z portal_1197 item_type_3 month_year_09_2026

Data for Switching on photoreactivity in Ti4-oxo clusters by increasing the size of 1,n-alkane diolate bridging ligands Ashwani Chikara (25045789) Alexander R. Veale (25045792) Stephen E. Brown (24989110) Jack Matthew Woolley (8774531) Frank De Proft (7474127) Sebastian D. Pike (1314372) Migrated from ePrints A series of new isostructural Ti-oxo clusters containing bridging bidentate 1,n-alkane diolate ligands with the formula [Ti4O4(O2PR2)4{O(CH2)nO}2] (R = Ph, n = 2–5; R = Cy, n = 2–4) were prepared by an alkoxide exchange strategy. The cluster with the 1,5-pentane diolate ligand undergoes productive photoredox chemistry in solution under UV light, resulting in the oxidation of one end of the alkane diolate, and subsequent cyclisation into the lactone tetrahydro-2H-pyran-2-ol, along with formation of a two-electron reduced Ti-oxo cluster stabilised by pyridine. Clusters with smaller bridging alkane diolates show no productive photoredox reactivity, except for R = Cy, n = 3, in which the photoredox products are unstable to further redox processes. Ultrafast electronic absorption spectroscopy studies reveal that all clusters undergo a similar initial photoexcitation step, therefore, productive redox pathways are controlled by the availability of a suitable transition state for rapid proton-coupled electron transfer from the initially generated pendant alkane diolate radicals {Ti–O(CH2)nO˙}. This is dependent on the flexibility (i.e. size) of the 1,n-alkane diolate ligand backbone. Interestingly, the productive photoredox pathway of the 1,5-pentane diolate cluster is turned off when the flexibility of the cluster is restricted in the single crystal phase.<br><br>Data included in and supporting the published article. Includes, DFT, NMR spectroscopy, and UV spectroscopy raw and/or processed data. 2025-11-27T00:00:00Z Dataset Dataset 10.82444/warw.33908266.v1 https://figshare.com/articles/dataset/Data_for_Switching_on_photoreactivity_in_Ti4-oxo_clusters_by_increasing_the_size_of_1_n-alkane_diolate_bridging_ligands/33908266 CC BY 4.0