State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002, Fuzhou, P.R. China.
Angew Chem Int Ed Engl. 2016 Apr 18;55(17):5160-5. doi: 10.1002/anie.201510455. Epub 2016 Mar 9.
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.
通过稳定的膦酸酯稳定的钛氧簇的不稳定配位位点，成功地引入了 14 个 O-供体配体，而不改变簇核。有机物种的吸电子效应逐渐增加，使得 {Ti6} 配合物的能带隙逐渐减小。然后通过使用双功能 O/N-供体配体引入过渡金属离子，将这些 {Ti6} 簇组装成聚合结构。所应用的金属离子的配位环境对其可见光吸收有显著影响。上述结构功能化还调节了这些簇的光催化 H2 产生活性。这项工作对钛氧簇进行了系统的能带工程研究，这不仅对其未来的光催化应用很重要，而且对更好地理解结构-性质关系也很重要。
