Control of Bridging Ligands in [(V2O3)2(RXO3)4⊂F]− Cage Complexes: A Unique Way To Tune Their Chemical Properties

In this work, the new organic–inorganic hybrid compound Ph4P­[(V2O3)2(PhAsO3)4⊂F] (VAsF) has been prepared and characterized by single-crystal XRD and multinuclear magnetic resonance (1H, 19F, 31P, and 51V). Redox properties and thermal stability have been investigated by EPR, cyclic voltammetry, and thermal analysis in comparison to its Ph4P­[(V2O3)2(PhPO3)4⊂F] (VPF) analogue. The VAsF cluster has a lower redox potential and higher electrochemical stability in solution, while it is thermally less stable in the solid state. Density functional theory (DFT) calculations showed that the difference in the redox potential is due to the different electron affinities of VPF and VAsF. With this approach of modifying the type of the ligand of the molecular vanadium cage, we hope to enhance the utility of such compounds as building blocks for the design of new hybrid materials with desirable properties.