New crystalline 1D/2D/3D indium selenides directed by piperidine and auxiliary solvents

The construction of cluster-based crystalline chalcogenide structures through the traditional solvothermal method relies on synergistic control of precursors, template cations and auxiliary solvents. Generally, the combination of metal precursors plays a crucial role in controlling the size of clusters, while organic templates and auxiliary solvents usually contribute to the type of clusters and architecture of the framework. Decades of synthetic efforts have been mainly devoted to expanding organic amine templates for constructing new structures. However, the important role of auxiliary solvents in enriching the chalcogenide family is usually disregarded. Reported here are several new crystalline In-Se compounds (ISP-1 to 4) with different dimensions, obtained by elaborately regulating auxiliary solvents under the direction of the same organic template, piperidine. Of these four structures, ISP-1 is constructed by irregular supertetrahedral clusters, giving a novel 2D structure with a corner-shared single Se atom and In₂Se₃ five-member ring as linkers; ISP-2 has a 1D structure composed by interlinked In₂Se₃ five-member rings; ISP-4 is constructed by supertetrahedral T2 clusters exhibiting an uncommon zeolite-like mog network.