Metallosupramolecular chemistry

Armspach D, Constable E C, Diederich F, Housecraft C E and Nierengarten J-F 1996 Bucky-ligands fullerene-substituted oligopyridines for metallosupramolecular chemistry J. Chem. Soc., Chem. Commun. 2009-10... 

Suitably substituted diazines also form chelate complexes, e.g. 2,3,5,6-tetrakis(a-pyridyl)pyrazine yields red tridentate complexes with Fe11. In the fast development of metallosupramolecular chemistry, many other polydentate ligands, based on 2,2 -bipyridyl units, have been obtained and studied (94CI(L)56). Thus, two molecules of oligopyridine (58) interact with various metal ions (Fe2+, Co2+, Cu2+ etc.) to form a double-helical [M2L2]4+ complex in which each metal is bonded to a tridentate region from each ligand. 

Most of sentiments expressed in the preface to the earlier edition of this book still hold. In the past five years metal-directed chemistry and the use of metal ions to control the stereochemical course of reactions have undergone something of a renaissance. The interface of inorganic and organic chemistry is found in supramolecular chemistry. It is true to say that an understanding of the interactions between metal ions and ligands is at the basis of much contemporary supramolecular and metallosupramolecular chemistry. 

Dithiocarbamate ligands have some structural similarities with carboxylates and their coordination chemistry has been explored extensively. Interestingly, their application in metallosupramolecular chemistry is almost unexplored so far, and there are only three reports on structurally characterized macrocycles derived from bis(dithiocarbamates) (Figure 2.5.12)." ... 

In addition to calixarenes which have been made water-soluble as new inverse phase-transfer catalysts [85], novel ligands have been designed, based on a cydo-propene moiety bearing pyridyl substituents and called [hexakis(2- or 3-pyridyl) 3 -radialene] 37. A metallosupramolecular chemistry is envisioned by the authors and the solubility in water and their stability offer innovative perspectives [86]. 

The concepts of molecular recognition, complementarity, pre-organization and predisposition and self-assembly are fundamental to, and a recurrent theme in, supramolecular and metallosupramolecular chemistry. 

Constable, E.C. (1994) Metallosupramolecular chemistry Chem. Ind., 56-59 Constable, E.C, Cargill Thompson, A.M.W. and D.A. Tocher (1992) Into the third dimension of coordination chemistry towards starburst arrays in Supramolecular Chemistry Eds Balzani, V. and De (Zola, L. Klewer Academic Press, Dordrecht 219-233 Constable, E.C, Cargill Thompson, A.M.W. and D.A. Tocher (1992) Synthesis, characterisation and spectroscopic properties of ruthenium(II)-2,2 6, 2"-terpyridine coordination triades. X-Ray structures of 4 -(A,A-dimethylamino)-2,2 6, 2"-terpyridine and w(4 -(A,A-dimethylamino)-2,2 6, 2"-terpyridine)ruthenium(II) hex uoro-phosphate acetonitrile solvate New J. Chem., 16, 855-867 Krohnke, F (1976) The specific synthesis of pyridines and oligopyridines Synthesis, 1-24... 

The synthesis and properties of ruthenium phthalocyanines, RuPcs, have been well studied over the last 30 years, but only recently they have been rediscovered for their potential application in metallosupramolecular chemistry. Basically, RuPcs are different from ZnPcs in their tendency to form stronger complexes with basic sp nitrogen atoms (pyridine and imidazole) and in the possibility to form complexes on one side or on both sides of the macrocycle. Another interesting point of ruthenium phthalocyanines resides in the longer lifetime of their radical-ion-pair state when compared to that of zinc phthalocyanines. Thus, all things being equal, RuPcs display a richer potential for supramolecular chemistry than ZnPcs. 

A widely studied Unkage in metallosupramolecular chemistry comprises terpyridine units, which form stable metal... 

Keywords Catalysis Click chemistry Metallosupramolecular chemistry... 

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