Does the Central Nitrogen Atom Make a Difference? A Comparison of Non‐Coordinating Pyridine and Benzene Spacers in Multitopic Ligands

Abstract In metal coordination compounds of the divergent ligands 4,2′:6′,4“‐terpyridine and 3,2′:6′,3”‐terpyridine and their 4′‐functionalized derivatives, the central pyridine ring of the 4,2′:6′,4“‐terpyridine and 3,2′:6′,3”‐terpyridine domains is non‐coordinated. We present an overview of data from the Cambridge Structural Database to assess whether there are structural similarities between the coordination compounds of 4,2′:6′,4“‐tpy and 1,3‐di(pyridin‐4‐yl)benzene, and between 3,2′:6′,3”‐tpy and 1,3‐di(pyridin‐3‐yl)benzene. Based upon structurally characterized compounds, it emerges that the coordination chemistry of ligands including one or more 4,2′:6′,4“‐terpyridine or 3,2′:6′,3”‐terpyridine metal‐binding domains is more abundantly exemplified than that of corresponding ligands based upon 1,3‐di(pyridin‐4‐yl)benzene and 1,3‐di(pyridin‐3‐yl)benzene. We provide an overview of metallamacrocycles and cages, 1D‐coordination polymers and 2D‐ and 3D‐networks.