Ligand-functionalized and ligand-bridged or organyl-separated chalcogenido metalate-based clusters

Pseudotetrahedral Organotin-Capped Chalcogenidometalate Supermolecules with Optical Limiting Performance

“…Dense-phase metallic chalcogenides are highly esteemed as advanced solid-state materials, representing an ever-growing area of research. − With a focus on reticulate chemistry, cluster-based open-framework chalcogenidometalates have been developed to integrate both porosity and semiconducting nature. − Crystallographically characterized chalcogenidometalate clusters are of significant importance both fundamentally and technologically and have thus garnered considerable attention in recent years. − There has been a fast-paced development of metal chalcogenide clusters over the past two decades, leading to the emergence of two distinct branches: noble metal Au/Ag thiolate aggregates, , and regularly shaped clusters based on nonprecious metals. − The supertetrahedral clusters are particularly noteworthy among the latter group of clusters due to their resemblance to structurally precise fragments of the cubic ZnS (one of the dense phases), termed as T n , where n denotes the number of metal layers. ,, Other supertetrahedral series published include penta (P n , an assemblage of four T n clusters capped via sharing triangular faces onto one anti-T n cluster in which the positions of cations and anions are exchanged), , capped (C n , conceptually constructed by a T n core covered by a single layer of vertex-sharing tetrahedral units and further completed by hexagonal, barrelanoid cages at the vertexes), , hierarchical (T m , n ), , octahedron-centered (T-O n ), and oxygen-stuffed (O-T n ) , types which can be derived from T n . These clusters exhibit distinct properties associated with their semiconductor nature, quantum-confinement effect, inversion-symmetry-free geometry, and nonlinear optical (NLO) response. − …”