A ferrocenecarboxylate-functionalized titanium-oxo-cluster: the ferrocene wheel as a sensitizer for photocurrent response

作者：Fan, Yang^*; Cui, Ying; Zou, Guo-Dong^*; Duan, Rui-Huan; Zhang, Xu; Dong, Yu-Xiang; Lv, Hai-Ting; Cao, Jun-Tao^*; Jing, Qiang-Shan

来源：Dalton Transactions, 2017, 46(25): 8057-8064.

DOI：10.1039/c7dt01756a

• METAL-ORGANIC FRAMEWORK
• SOLAR-CELLS
• POLYOXOTITANATE NANOCLUSTERS
• DYE
• STABILITY
• SURFACE
• CAGES
• ALKOXIDE

Sensitized titanium-oxo clusters (TOCs) have attracted growing interest. However, reports on TOCs incorporated with a metal complex as photosensitizers are still very rare. In the present work, the organometallic complex ferrocene was used as a sensitizer for a titanium-oxo cluster. A ferrocenecarboxylate-substituted titanium-oxo cluster [Ti-6(mu(3)-O)(6)(OiPr)(6)(O(2)CFc)(6)] (Fc = ferrocenyl) was synthesized and structurally characterized, in which the ferrocene wheel performs as a sensitizer for photocurrent response. For comparison, naphthalene-sensitized titanium-oxo clusters [Ti-6(mu(3)-O)(6)(OiPr)(6)(NA)(6)] (NA = 1-naphthoate) and [Ti-6(mu(3)-O)(6)(OiPr)(6)(NA)(6)] (NA = 1-naphthylacetate) with the same {Ti-6} core structure were also synthesized. The structures, optical behaviors, electronic states and photoelectrochemical properties of these sensitized {Ti6} clusters were investigated. It is demonstrated that the introduction of ferrocene groups into the titanium-oxo cluster significantly reduces the band gap and enhances the photocurrent response in comparison with the naphthalene-sensitized clusters. The substantially reduced band gap of the ferrocene-sensitized cluster was attributed to the introduction of Fe(II) d-d transitions and the possible contribution from the Fc ->{Ti-6} charge transfer. For the naphthalene-sensitized clusters, the better electronic coupling between the dye and the {Ti-6} core in the 1-naphthoate (NA) substituted cluster results in higher photoelectrochemical activity.

• 出版日期2017-7-7
• 单位中国科学院福建物质结构研究所; 信阳师范学院