The Synthesis and Ion Bindings of Synthetic Multidentate Macrocyclic Compounds.

More than a quarter of a century after the first metal template synthesis of a [2]catenane in Strasbourg, there now exists a plethora of strategies available for the construction of mechanically bonded and entwined molecular level structures. Catenanes, rotaxanes, knots and Borromean rings have all been successfully accessed by methods in which metal ions play a pivotal role. Originally metal ions were used solely for their coordination chemistry; acting either to gather and position the building blocks such that subsequent reactions generated the interlocked products or by being an integral part of the rings or "stoppers" of the interlocked assembly. Recently the role of the metal has evolved to encompass catalysis: the metal ions not only organize the building blocks in an entwined or threaded arrangement but also actively promote the reaction that covalently captures the interlocked structure. This Review outlines the diverse strategies that currently exist for forming mechanically bonded molecular structures with metal ions and details the tactics that the chemist can utilize for creating cross-over points, maximizing the yield of interlocked over non-interlocked products, and the reactions-of-choice for the covalent capture of threaded and entwined intermediates.

Strategies and tactics for the metal-directed synthesis of rotaxanes, knots, catenanes, and higher order links.

Ligand environment and the structure of schiff base adducts and tetracoordinated metal-chelates

Coordination compounds of copper, nickel and iron with Schiff bases derived from hydroxynaphthaldehydes and salicylaldehydes

Thin films of transition metal complex-based redox polymers are electrodeposited on electrodes via application of fixed or cycled potential. When hydrated, an electrodeposited film conducts electrons by electron exchange between backbone-bound, but mobile, functional segments of its redox polymer constituents. These functional segments, or redox complexes, have labile ligands, such as chloride anions, for example, in their inner coordination spheres. The backbones of the redox polymers have strongly coordinating ligands, such as pyridine- or imidazole-containing functions, for example, which are generally not coordinated prior to deposition. Electrodeposition results from coordinative crosslinking by exchange of labile ligands and strongly coordinating ligands between polymer chains, provided sufficient functional segments of the redox polymers are present at the electrode surface. When a biological macromolecule or protein, such as a redox enzyme, is added to the solution from which the redox polymer is electrodeposited, it is co-electrodeposited on the electrode surface. When the co-deposited film contains redox enzymes, for example, the modified electrode may be used to catalyze the electrooxidation or electroreduction of substrates of the enzymes. Electrodes modified according to the invention also have application in chemical or biological assays.

Electrodeposition of redox polymers and co-electrodeposition of enzymes by coordinative crosslinking

Porphyrin-annulene redox-related ligand pair. Electrochemical synthesis and characterization of the reduction products of the cobalt, copper, and nickel complexes of a tetraaza[16]annulene

Describes the design and experimental use of a variable-temperature Faraday magnetic balance.

A variable-temperature Faraday magnetic balance

Nickel(II) and copper(II) complexes containing new monocyclic and polycyclic ligands derived from the cyclotetrameric Schiff base of o-aminobenzaldehyde

Mononuclear and oxide-bridged binuclear iron(III) complexes containing the cyclic tetradentate Schiff base derived from o-aminobenzaldehyde

Coordination complexes of niobium and tantalum. VII. Preparation and infrared spectra of oxygen-18 labeled terminal and bridging monoxoniobium(V) complexes and the course of coordinated alkoxo group hydrolysis in mixed-ligand niobium complexes

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