4,2':6',4''-Terpyridines: diverging and diverse building blocks in coordination polymers and metallomacrocycles.

4,2':6',4''-Terpyridine (4,2':6',4''-tpy) is one of the less well documented isomers of the well-established bis-chelating 2,2':6',2''-terpyridine. The N-donors of the outer rings in 4,2':6',4''-tpy subtend an angle of 120°, leading to a description of 4,2':6',4''-tpy as a divergent ligand. Because it typically binds metal ions through the outer N-donors only, 4,2':6',4''-tpy is an ideal linker for combination with metal nodes (often geometrically flexible d(10) ions) in coordination polymers and metallomacrocyclic complexes. The facile functionalization of terpyridines in the 4'-position allows access to a suite of 4'-X-4,2':6',4''-tpy ligands in which the 4'-substituent, X, can be selected to assist in directing the metal-ligand assembly process. This overview of recent advances in the chemistry of 4,2':6',4''-tpy and its 4'-substituted derivatives looks at relationships within a series of chiral polymers, competition between the formation of metallocyclic complexes versus polymers, and the use of extended aryl systems to encourage the formation of coordination polymers in which π-stacking of arene domains dominates in the assembly process. Use of metal(ii) acetates is key to the formation of paddle-wheel and larger cluster nodes that direct the assembly of both predetermined and unexpected architectures.