Divergent 4,2′:6′,4′′- and 3,2′:6′,3′′-terpyridines as linkers in 2- and 3-dimensional architectures

Abstract

This Highlight illustrates the strategies applied to encourage the formation of 2- and 3-dimensional metal–organic architectures as opposed to 1-dimensional chains using 4,2′:6′,4′′- and 3,2′:6′,3′′-terpyridines as organic linkers.

Coordination Behaviour of 1-(4,2′:6′,4′′-terpyridin-4′-yl)ferrocene and 1-(3,2′:6′,3′′-terpyridin-4′-yl)ferrocene: Predictable and Unpredictable Assembly Algorithms

“…[22,31] During the course of our investigations of the coordination chemistry of the ferrocenyl-functionalized 4,2':6',4''-and 3,2':6',3''-terpyridines shown in Scheme 2, Tian and coworkers reported that 2 reacts with ZnCl2 and ZnBr2 to give the discrete metallohexacycles 9…”

What a difference a tail makes: 2D → 2D parallel interpenetration of sheets to interpenetrated nbo networks using ditopic-4,2′:6′,4′′-terpyridine ligands

“…1,2,3 A 4,2':6',4''-tpy ligand presents a V-shaped building block, coordinating only through the outer N-donors. 1,2 Kröhnke 4 or Wang and Hanan 5 synthetic methodologies permit ready functionalization of the 4'-position of the tpy unit. If the functional group is non-coordinating, the common assembly motifs for architectures supported by 4,2':6',4''-tpy ligands are 1D-chains and 2D-sheets depending upon the coordination geometry of the metal nodes.…”

“…If the functional group is non-coordinating, the common assembly motifs for architectures supported by 4,2':6',4''-tpy ligands are 1D-chains and 2D-sheets depending upon the coordination geometry of the metal nodes. 1,2 The introduction of coordinatively non-innocent domains such as pyridyl 6 or carboxylate 7 moieties is a proven approach to increasing the dimensionality of 4,2':6',4''-tpy-based coordination assemblies.…”

“…In contrast, combining 2 (Scheme 3) with ZnCl 2 or ZnBr 2 leads to 2D-sheets in which the ligands are the unique nodes. 13,14 While the (4,4) (2)}] n , and are threaded within the interpenetrated sheets. We have previously suggested that the long chains may assist in directing the assembly process.…”

4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

“…The coordination chemistry of divergent 4,2’:6’,4”-terpyridine (4,2’:6’,4”-tpy) and 3,2’:6’,3”-terpyridine ligands is now a mature field, with the former ligand in particular being increasingly employed as a building block for the assembly of coordination polymers and networks [1,2]. There are a few examples of 4,2’:6’,4”-tpy ligands acting in a monodentate mode [3,4,5,6,7] but, typically, 4,2’:6’,4”-tpy coordinates through the two outer nitrogen atoms, with the central nitrogen atom non-coordinated.…”