From Metal‐Metal Bonding to Supra‐Metal‐Metal Bonding Directed Self‐Assembly: Supramolecular Architectures of Group 10 and 11 Metals with Ligands from Mono‐ to Poly‐Pyrazoles

The supramolecular architectures of pyrazole ligands with polynuclear metal centers have established a wide variety of constructing motifs. This review focuses on the metal‐metal bonding and Supra‐Metal‐Metal Bonding directed self‐assembly of supramolecular architectures of pyrazole ligands ranging from simple mono‐pyrazoles and derivatives to bipyrazoles and polypyrazoles with group 10 and 11 elements. The utility of the constructing motifs (μ‐pyrazolato‐N,N′)2 doubly‐bridged dimetal corners in the metal‐metal‐bonding directed self‐assembly approaches with spontaneous deprotonation from bipyrazole to tripyrazole and tetrapyrazolyl calix[4]arene ligands, metallomacrocyclic and cage‐like complexes have been synthesized. The proton switching programmable self‐assembly strategy using pyrazole‐based bifunctional ligands has been developed by Yu. They have obtained organic homo‐ or hetero‐metallic supramolecular complexes from macrocycles, cages, to one dimensional polymers.