Organically directed heterometallic chalcogenidometalates containing group 12(II)/13(III)/14(IV) metal ions and antimony(III)

•Construct new structures by combination of regular- and pseudo-polyhedral geometries.•Summarize the organically directed 12(II)/13(III)/14(IV)-Sb(III)-Q chalcogenidometalates.•Analyze the structural features by using “building unit” concept.•Classify the structure-directing roles of amines in the lattice formation.•Discuss the property studies on ion-exchange, photocatalysis, and NTE.

Crystalline chalcogenidometalates are a class of solid-state materials with great significance for both basic science and technological applications. The strong dependence of their functionalities on the crystal structures has led to increasing efforts in preparing new compounds with targeted structural features. It has proven to be a powerful structure-construction strategy to combine the elements with different coordination behaviors into one single crystal lattice. This review focuses on an emerging and effective method to construct chalcogenidometalates, namely combining the regular-polyhedral {M(Q/N)x} (M = 12(II) of Zn, Cd, Hg; 13(III) of Ga, In; 14(IV) of Ge, Sn; Q = S, Se; N = N donor atom of ligand; x = 2, 3, 4, 5, 6) and the pseudo-polyhedral ψ-{SbQx} (Q = S, Se; x = 3, 4) in the presence of neutral/protonated amine molecules and metal–amine complexes. We analyze systematically the coordination characteristics of PBUs and the condensation of PBUs to form SBUs or even TBUs. Based on the structural survey and comparison, the significant contributions of intrinsic coordination behavior of metal centers to the novelty of the overall solid-state structures are revealed. In addition, the crucial structure-directing roles of amines in the formation of these chalcogenidometalates are discussed in detail. Finally, the advances in the functionalization of these materials for heavy metal ion-exchange, photocatalysis, and NTE are presented, as well as structure- and composition-property relationships.

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