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

We report here the synthesis of a ferrocene-functionalized {Ti22Fc4} cluster with a ‘dimer-of-clusters’ topology, which represents the largest Ti-oxo cluster (TOC) modified with organometallic groups ever reported. The exact assembly path of {Ti22Fc4} can be inferred from its two substructures, {Ti11Fc2} and {Ti5Fc}, which can also be synthesized independently through subtle changes in reaction conditions. Furthermore, we used these clusters as photocatalysts, and have studied, for the first time, the photocatalytic activity of TOCs in the oxidative coupling of amines.