Ligand Design in Multimetallic Architectures:  Six Lessons Learned

Abstract

Metallosupramolecular chemistry involves the use of combinations of organic ligands and metals for the construction of both discrete and polymeric aggregates. This Account describes some lessons that we have learned about aspects of ligand design in the course of our work in this area. Specifically, we recommend the incorporation of a diverse range of heterocyclic rings and arene cores within the ligands, as well as attention to symmetry considerations, and offer suggestions for the introduction of chirality and flexibility within the ligands and the exploitation of other weak interactions to assist self-assembly processes.

Crystal structure of dichloro[3-(pyridin-2-yl)-1H-pyrazol- 1-yl]propanamidezinc(II), ZnCl2(C11H12N4O)

“…In recent years, 3-(2-pyridyl)pyrazole-based ligands have been found for awide range of application in coordination chemistry, because they can act as bridging or chelating ligands and exhibit a series of intriguing structures and potential applications as functional materials [1,2]. Nowadays, much attention has been focused on the synthetic approach and the structural control of coordination architectures [3,4].…”

Chiral heterocyclic ligands. XIV. Control of directionality in silver coordination polymers through ligand design

“…4 An important requirement for these properties is that the material be non-centrosymmetric and we believe that the simplest approach to the synthesis of noncentrosymmetric coordination polymers is to employ chiral bridging ligands. 5 Furthermore, it has been stated that such effects can be amplified by the additional polarisation associated with directionality in the chain. 6 We have previously shown 7 that the homochiral C 2 -symmetric ligand 1 (scheme 1), consisting of a central pyrazine ring with two fused bornane groups, readily forms a linear 1-D silver coordination polymer.…”

Hierarchical assembly of discrete copper(ii) metallo-structures from pre-assembled dinuclear (bis-β-diketonato)metallocycles and flexible difunctional co-ligands

“…26 Further, the use of such non-planar co-ligands incorporating different donors (namely, secondary versus tertiary amines versus thioethers) also gives the potential for 'tuning' the coordination geometry adopted by the metal 27 and hence influence the outcome of the self-assembly process.…”