A ferrocenecarboxylate-functionalized titanium-oxo-cluster: the ferrocene wheel as a sensitizer for photocurrent response. Issue 25 (12th June 2017)

• Record Type: Journal Article
• Authors: Fan, Yang; Cui, Ying; Zou, Guo-Dong; Duan, Rui-Huan; Zhang, Xu; Dong, Yu-Xiang; Lv, Hai-Ting; Cao, Jun-Tao; Jing, Qiang-Shan
• Is Part Of: Dalton transactions. Volume 46:Issue 25(2017)
• Page Start: 8057
• Page End: 8064
• Publication Date: 2017-06-12
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt01756a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A ferrocenecarboxylate-functionalized titanium-oxo cluster [Ti6 (μ3 -O)6 (OiPr)6 (O2 CFc)6 ] was synthesized, in which the ferrocene wheel performs as a sensitizer for photocurrent response. Abstract : 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 [Ti6 (μ3 -O)6 (OiPr)6 (O2 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 [Ti6 (μ3 -O)6 (OiPr)6 (NA)6 ] (NA = 1-naphthoate) and [Ti6 (μ3 -O)6 (OiPr)6 (NAA)6 ] (NAA = 1-naphthylacetate) with the same {Ti6 } 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 → {Ti6 } charge transfer. For the naphthalene-sensitized clusters, the better electronic coupling between the dye and the {Ti6 } core in the 1-naphthoate (NA) substituted cluster results in higher photoelectrochemical activity.