title: Bandgap Engineering of Titanium-Oxo Clusters: Labile Surface Sites Used for Ligand Substitution and Metal Incorporation.
abstract: 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.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002, Fuzhou, P.R. China.
authors.forename: Jin-Xiu
authors.initials: JX
authors.lastname: Liu
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002, Fuzhou, P.R. China.
authors.forename: Mei-Yan
authors.initials: MY
authors.lastname: Gao
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002, Fuzhou, P.R. China.
authors.forename: Wei-Hui
authors.initials: WH
authors.lastname: Fang
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002, Fuzhou, P.R. China. LZhang@fjirsm.ac.cn.
authors.forename: Lei
authors.initials: L
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002, Fuzhou, P.R. China. zhj@fjirsm.ac.cn.
authors.forename: Jian
authors.initials: J
authors.lastname: Zhang
keywords: bandgaps; cluster compounds; labile coordination sites; ligand effects; titanium