Molecular self-assembly with modularization and directionality: Vector-manipulation at metal centers

The account highlights an important approach to supramolecular self-assembly via vector-manipulation at metal centers ranging from Werner-system to Cotton-system coordination compounds. The approach has been successfully employed in the architecture of container molecules like metal analogues of the bowl-shaped calixarenes and metal-linked calixarene-based carcerands and carceplexes. The concepts of metal vector and vector-manipulation at metal centers were further interpreted based upon the stereochemistry and trans- or cis-effect of ligands in the substitution reactions at metal centers.