Steerable\nStructural Evolvement and Adsorption Behavior\nof Metastable Polyoxovanadate-Based Metal–Organic Polyhedra

Promoting the advancement of the structure and function\nof metastable\nsubstances is challenging but worthwhile. In particular, how to harness\nthe entangled state and evolution path of labile porous structures\nhas been at the forefront of research in molecular self-assembly.\nIn this work, the metastable structures of polyoxovanadate-based metal–organic\npolyhedra (VMOPs) can be manually regulated, including separation\nof the interlocked aggregate by a ligand-widening approach as well\nas transformation from a tetrahedral to capsule-like scaffold via\na vertice-remodeling strategy. In these processes, intra- and intermolecular\nπ···π and C–H···π\ninteractions have been recognized as the primary driving forces. Besides\nbeing responsible for commanding the structural evolvement of VMOPs,\nsuch weak interactions were able to program their spatial arrangements\nand hence the adsorption performances for dye and iodine. The successful\nuse of such a weak force-dominated design concept beacons a feasible\nroute for customization of the function-oriented metastable structures.\nSeparation and transformation of the interlocked metastable VMOPs\nhave been achieved via the respective ligand-widening approach and\nvertice-remodeling strategy. Not only their structures but also adsorption\nfeatures could be well regulated by such a weak force-dominated design\nconcept.