Crystal engineering of multidimensional copper(I) and silver(I) coordination supermolecules and polymers with functions

Considerable progress has been made in recent years in controlling the assembly and orientations of individual molecules to create specific aggregates. It is the aim of this review to give an account of the latest developments in our groups with regard to construction of functional crystal metal complex supermolecules from self-assembly of copper(I) and silver(I) coordination compounds by intermolecular interactions as well as coordination bonds. Several approaches to such self-organization process have been highlighted. Spontaneous organization of hydrogen bonding and host-guest interactions in 3-cyano-6-methyl-2(1H)-pyridinone system result in the formation of three-dimensional channel structures and multi-fold interpenetrated diamondoid architectures by modification of hydrogen-bonding mode and distances. Control of effective aromatic stackings between polymeric chains assembles simple phenazine and benzothiadiazole building blocks into well-organized, multidimensional honeycomb and graphite structures. Manipulation of strong interchain S...S contacts in sulfur-rich tetrathiafulvalene derivative system creates a unique bookshelf type frameworks. Employment of multi-coordination sites of the ligands in pyrazine, dithienylethene and dithiaparacyclophane systems generates a number of novel infinite-sheet and chain metal polymers with the potential to serve as functional supramolecular devices.