The photochemistry of V(V) tartrate clusters (V4O8tart2) in water has been characterized, showing conversion to purple V(IV) species (V2O2tart2). During this photochemical transformation, the reduction of the V(V) is accompanied by oxidation of the tartrate ligand, with some oxidative decarboxylation to form CO2. This reaction can be reversible in air, if excess tartrate is around to re-form the tetrameric clusters. We have harnessed this photochemistry to create photoresponsive materials that feature V(V) coordination to polysaccharides. In these materials, the V(V) coordination leads to an increase in the stiffness of the materials, and changes the assembly of the polysaccharides as visualized with SEM. In addition, these materials show analogous photochemistry to the V(V) tartrate clusters, with a color change from yellow to blue/purple.

V(V) carboxylate complexes: Photochemistry and materials applications

ACS Spring 2022

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