Macrocyclic copper(I) and silver(I) pyrazolates: Principles of supramolecular assemblies with Lewis bases

Macrocyclic copper(I) and silver(I) pyrazolates represent an important class of coordination compounds used in numerous fundamental areas, such as acid-base chemistry, metallophilic bonding, supramolecular assemblies. In this review we discuss the host-guest complexes of the macrocyclic copper(I) and silver(I) pyrazolates with a wide range of organic and organometallic bases possessing hydride, halide, carbonyl and π-electronic ligands. The purpose of our review is to show the relationship between the solution and solid state chemistry of the target complexes using our approach. The study in solution takes into account a competition between different basic sites of the guest and selectivity of trinuclear macrocycles complexation with certain basic centers. It also allows determining the complexes compositions and their thermodynamic parameters (formation constants, ΔH°, ΔS°). Peculiar features of crystal packing depending on the base type, the complex strength, and the presence of a secondary basic center are summarized and analyzed in this review. This analysis shows how the information on the complexes structure and stability in solution can be used to predict and control the supramolecular architecture in the solid state.