Bandgap Engineering of Titanium–Oxo Clusters: Labile Surface Sites Used for Ligand Substitution and Metal Incorporation

Through the labile coordination sites of a robust phosphonate-stabilized titanium-oxo cluster, 14 O-donor ligands have been successfully introduced without changing the cluster core. The increasing electron-withdrawing effect of the organic species allows the gradual reduction of the bandgaps of the {Ti6 } complexes. Transition-metal ions are then incorporated by the use of bifunctional O/N-donor ligands, organizing these {Ti6 } clusters into polymeric structures. The coordination environments of the applied metal ions show significant influence on their visible-light adsorption. Both the above structural functionalizations also tune the photocatalytic H2 production activities of these clusters. This work provides a systematic bandgap engineering study of titanium-oxo clusters, which is important not only for their future photocatalytic applications, also for the better understanding of the structure-property relationships.