Self-Assembly of Chiral Ferrocene-Functionalized Polyoxotitanium Clusters for Photocatalytic Selective Sulfide...

Here, we systematically studied the self-assembly behavior of chiral polyoxytitanium clusters for the first time. Through the cooperative assembly of ferrocenecarboxylic acid and ketoxime ligands, we successfully incorporated the planar chirality of ferrocene (Fc) into the layered {Ti₅} building blocks. The resulting {Ti₅Fc} clusters can be used as structural units to assemble into large ordered structures in various ways; either a pair of {Ti₅Fc} enantiomers are bridged by organic adhesive to form sandwich structures or two homochiral {Ti₅Fc} units participate in the assembly to form the large clusters. Depending on the assembly modes, the chirality of {Ti₅Fc} can be transferred to large nanoclusters or disappear to form mesostructures. The difference of the assembly modes between the {Ti₅Fc} units can also tune the photoelectric activity of the resulting clusters, which has been verified by using {TiFc-6/7} as catalysts for photocatalytic selective sulfide oxidation. This work not only is an important breakthrough in the study of the self-assembly of chiral nanoclusters but also provides an important reference for understanding of chiral transfer on the nanoscale.