Accurate assembly of ferrocene-functionalized {Ti22Fc4} clusters with photocatalytic amine oxidation activity

Abstract

We report here the synthesis of a ferrocene-functionalized {Ti22Fc4} cluster with a ‘dimer-of-clusters’ topology, which represents the largest Ti-oxo cluster (TOCs) modified with organometallic groups yet to be reported. The...

Ferrocene-sensitized titanium-oxo clusters with effective visible light absorption and excellent photoelectrochemical activity

“…1f). Similar to that of the reported ferrocene-sensitized Ti-oxo clusters, 57–61 the ten Ti atoms in cluster Ti 10 Fcdc 2 are also six-coordinated with a slightly distorted octahedral geometry (Fig. 1g).…”

“…Furthermore, Ti1, Ti2, and Ti3 in the Ti 4 (μ 3 -O) 2 unit are also connected to two oxygen and one nitrogen of diisopropanolamine, and the Ti–O core of cluster Ti 8 Fcdc 4 is connected with twelve terminal –O i Pr groups. Different from the reported {Ti 22 Fc} structure, 61 the Fcdc ligand in Ti 8 Fcdc 4 exhibits two coordination modes, and this phenomenon is rare in Ti-based coordination compounds. Similar to that of reported ferrocene-sensitized Ti-oxo clusters, 56–60 Ti atoms (Ti2, Ti3, and Ti4) in the Ti 4 (μ 3 -O) 2 unit are also six-coordinate with a slightly distorted octahedral geometry configuration, while the Ti1 atom is seven-coordinate with a pentagonal bipyramid coordination environment (Fig.…”

“…The extended visible absorption band is mainly induced by the charge transfer from the Fcdc ligands to the Ti-oxo core, as that for the reported Ti-oxo clusters functionalized by ferrocene ligands. 56–61 According to the Kubelka–Munk function F ( R ) = (1 − R ) 2 /2 R , the estimated band gap energy of clusters Ti 8 Fcdc 4 and Ti 10 Fcdc 2 is about 2.05 and 2.10 eV, respectively (Fig. 3b).…”

“…53 However, to the best of our knowledge, there are only a few examples of Ti-oxo clusters with ferrocene-derived functional ligands being reported. 54–61 Dai and Fan's groups made a great contribution in this field and synthesized a series of ferrocene-sensitized Ti-oxo clusters. 55–59 More recently, Lan and co-workers reported the synthesis and CO 2 photoreduction of ferrocene-sensitized Ti-oxo clusters.…”

“…60 It is worth mentioning that Liu's group synthesized the biggest ferrocene-sensitized {Ti 22 Fc 4 } cluster. 61 Despite the above successful cases, the diversity of ferrocene-sensitized Ti-oxo clusters applied in structural model research studies is still unknown. In addition, the structure–property relationship of ferrocene-sensitized Ti-oxo clusters is worth further investigation.…”