Issue 21, 2022

Assembly of cyclic ferrocene-sensitized titanium-oxo clusters with excellent photoelectrochemical activity

Abstract

The development of crystalline titanium-oxo clusters has made great progress in recent years. However, the geometric assembly of titanium-oxo clusters is still very challenging. Herein, we report the assembly of two cyclic titanium-oxo clusters with ferrocene connectors, formulated as Ti123-O)4(Fcdc)4(OiPr)32·0.5CH2Cl2 (Fcdc = 1,1′-ferrocenedicarboxylic acid; Ti12Fcdc4) and Ti182-O)63-O)6(Fcdc)2(L1)2(L2)4(OiPr)34·2HOiPr (L1 = isonicotinic acid; L2 = salicylhydroxamic acid; Ti18Fcdc2). Single-crystal X-ray diffraction studies demonstrate that ferrocene with two carboxylic arms can adhere to the surface of {Ti6} and/or {Ti3} units, resulting in fascinating cyclic structures of Ti12Fcdc4 and Ti18Fcdc2. Notably, ferrocene ligands can not only serve as connectors to induce the geometric assembly of Ti-oxo clusters, but can also act as photosensitizers to greatly improve the light absorption behavior of the resulting compounds. Furthermore, the DFT calculation results suggest that the HOMO → LUMO transition mainly involves ferrocenyl group → Ti-oxo core charge transfer. Using the two ferrocene-containing clusters as electrode precursors, both electrodes exhibited excellent photocurrent responses. Our work opens a new way for the geometric assembly of titanium-oxo clusters and also contributes to the deep understanding of the structure–property relationships of sensitized Ti-based materials.

Graphical abstract: Assembly of cyclic ferrocene-sensitized titanium-oxo clusters with excellent photoelectrochemical activity

Supplementary files

Article information

Article type
Research Article
Submitted
08 maí 2022
Accepted
31 ágú. 2022
First published
01 sep. 2022

Inorg. Chem. Front., 2022,9, 5616-5623

Assembly of cyclic ferrocene-sensitized titanium-oxo clusters with excellent photoelectrochemical activity

C. Wang, N. Chen, S. Wang and F. Kong, Inorg. Chem. Front., 2022, 9, 5616 DOI: 10.1039/D2QI01007K

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