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.

Ligand Design in Multimetallic Architectures: Six Lessons Learned

Coordination chemistry with pyrazole-based chelating ligands: molecular structural aspects

The synthesis and coordination chemistry of 2,6-bis(pyrazolyl)pyridines and related ligands — Versatile terpyridine analogues

Aromatic nitrogen heterocycles as bridging ligands; a survey

This Perspective summarises the chemistry of the pyrazole ring, and reviews the metal coordination modes adopted by 1H-pyrazoles and their anions. Pyrazolide anions are probably the most versatile ligands in coordination chemistry, with 20 different terminal or bridging coordination modes having been identified so far. Metal cluster compounds supported by pyrazolido ligation are surveyed, concentrating on those reported during the past ten years. Highlights include the wide structural diversity in apparently simple main group pyrazolides; luminescence and charge-transfer complexes in coinage metal pyrazolide clusters; the use of robust metal pyrazolide clusters to construct liquid crystals, supramolecular materials and metal–organic frameworks; and supramolecular complexes formed by pyrazolide-supported metallacrowns.

Pyrazoles and pyrazolides—flexible synthons in self-assembly

Chiral heterocyclic ligands. Part IV. Synthesis and metal complexes of 2,6-Bis(pyrazol-1-ylmethyl)pyridine and chiral derivatives

The syntheses of the pyrazolylmethylpyridines (5a-c), their chiral derivatives (7) and (8), and the chiral methylenebisindazoles (9)-(11) are reported. These bidentate ligands form stable 1 : 1 complexes with PdCl2. A single-crystal X-ray structure determination of dichloro [(4S,7R)-7,8,8-trimethyl-2-(pyridin-2-ylmethyl)-4,5,6,7-tetrahydro-4,7-methano-2H-indazole]palladium(II),(16), is also reported.

Chiral Heterocyclic Ligands. II. Synthesis and Palladium(II) Complexes of Chiral Pyrazolylmethyl-Pyridines and Pyrazolylmethyl-Pyrazoles

Chiral heterocyclic ligands: III. A structural study of the cyclopalladation of (4S, 7R)-7,8,8-trimethyl-1-phenyl-4,5,6,7-tetrahydro-4,7-methano-1H-indazole

The syntheses of 23 new chelating ligands are described. Most of these ligands are derived from the chiral pyrazole (1) which has been linked to a variety of heterocycles , namely pyridine, pyrimidine, pyridazine, isoxazole , benzimidazole, thiophen and furan. In certain cases the parent achiral analogues have also been prepared. Preliminary studies of the coordination chemistry of these ligands with selected transition metals have been carried out. The X-ray crystal structures of palladium complexes of isoxazole- and thiophen-containing ligands have also been determined.

Chiral Heterocyclic Ligands. VIII. Syntheses and Complexes of New Chelating Ligands Derived From Camphor

As part of ongoing studies of new chiral heterocyclic ligands and of pyrazole-containing ligands, we now report the syntheses and properties of these new ligands that were prepared from the homochiral camphor-derived pyrazole

A. A. Watson

Papers

Chiral heterocyclic ligands. Part IV. Synthesis and metal complexes of 2,6-Bis(pyrazol-1-ylmethyl)pyridine and chiral derivatives

Chiral Heterocyclic Ligands. II. Synthesis and Palladium(II) Complexes of Chiral Pyrazolylmethyl-Pyridines and Pyrazolylmethyl-Pyrazoles

Chiral heterocyclic ligands: III. A structural study of the cyclopalladation of (4S, 7R)-7,8,8-trimethyl-1-phenyl-4,5,6,7-tetrahydro-4,7-methano-1H-indazole

Chiral Heterocyclic Ligands. VIII. Syntheses and Complexes of New Chelating Ligands Derived From Camphor

Chiral heterocyclic ligands. 7. Syntheses of some chiral 2,6-di-N-pyrazolylpyridines