Functionalised Terpyridines and Their Metal Complexes—Solid-State Interactions

Abstract

Analysis of the weak interactions within the crystal structures of 33 complexes of various 4′-aromatic derivatives of 2,2′:6′,2″-terpyridine (tpy) shows that interactions that exceed dispersion are dominated, as expected, by cation...anion contacts but are associated with both ligand–ligand and ligand–solvent contacts, sometimes multicentred, in generally complicated arrays, probably largely determined by dispersion interactions between stacked aromatic units. With V(V) as the coordinating cation, there is evidence that the polarisation of the ligand results in an interaction exceeding dispersion at a carbon bound to nitrogen with oxygen or fluorine, an interaction unseen in the structures of M(II) (M = Fe, Co, Ni, Cu, Zn, Ru and Cd) complexes, except when 1,2,3-trimethoxyphenyl substituents are present in the 4′-tpy.

Coordination Polymers and Metal-Organic Frameworks: Structures and Applications—A Themed Issue in Honor of Professor Christoph Janiak on the Occasion of His 60th Birthday

“…Harrowfield and coworkers provide a detailed analysis of the weak interactions in the single crystal structures of 33 metal(II) complexes incorporating twelve 4 -functionalized 2,2 :6 ,2 -terpyridine (tpy) ligands. The structural and packing details that are revealed in this investigation should be valuable in the future design of functional materials based on tpy [7]. While 2,2 :6 ,2 -terpyridine is the ubiquitous isomer of terpyridine, 3,2 :6 ,3 -terpyridine has been far less studied.…”