Premium
Bandgap Engineering of Titanium–Oxo Clusters: Labile Surface Sites Used for Ligand Substitution and Metal Incorporation
Author(s) -
Liu JinXiu,
Gao MeiYan,
Fang WeiHui,
Zhang Lei,
Zhang Jian
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201510455
Subject(s) - bifunctional , phosphonate , titanium , cluster (spacecraft) , photocatalysis , ligand (biochemistry) , metal , band gap , adsorption , chemistry , transition metal , metal ions in aqueous solution , ion , molecular engineering , materials science , inorganic chemistry , photochemistry , combinatorial chemistry , nanotechnology , catalysis , organic chemistry , biochemistry , receptor , optoelectronics , computer science , programming language
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 {Ti 6 } complexes. Transition‐metal ions are then incorporated by the use of bifunctional O/N‐donor ligands, organizing these {Ti 6 } 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 H 2 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.