Doping transition metals to modulate the chirality and photocatalytic activity of rare earth clusters

Abstract

In this paper, we report the successful assembly of achiral {Ln₆M} ([Ln₆M(μ₃-OH)₈(acac)₁₂(CH₃O)_x(CH₃OH)_y], Ln = La, M = Mn, Co, Fe) and chiral {Nd₉Fe₂} ([Nd₉Fe₂(μ₄-O)(μ₃-OH)₁₄(acac)₁₆(NO₃)(CH₃OH)₂(H₂O)₃]) rare earth clusters using achiral rigid ligands and a transition metal doping strategy. {Ln₆M} can be viewed as the fusion of two {Ln₃M} tetrahedrons by sharing vertices. {Nd₉Fe₂} results from the fusion of four {Ln₃M} tetrahedrons by vertice and edge sharing. The substitution of Ln with transition metal leads to changes in the coordination pattern around neighboring Ln, which triggers the switch of metal center chirality. This study demonstrates the potentiality of utilizing transition metal doping and rigid ligand to control the chirality of rare earth clusters. In addition, the photocatalytic CO₂ activity of these transition metal-doped rare earth clusters has been studied.