The ability of a broad range of N-heterocycles to act as very effective and stable complexation agents for several transition metal ions, such as cobalt(II), copper(II), nickel(II), and ruthenium(II), has long been known in analytical chemistry. This behavior was later utilized in supramolecular chemistry for the construction of highly sophisticated architectures, such as helicates, racks, and grids. The discovery of macromolecules by Staudinger in 1922 opened up avenues towards sophisticated materials with properties hitherto completely unknown. In the last few decades, the combination of macromolecular and supramolecular chemistry has been attempted by developing metal-complexing and metal-containing polymers for a wide variety of applications that range from filtration to catalysis. The stability of the polymer-metal complex is a fundamental requirement for such applications. In this respect, the use of bi- and terpyridines as chelating ligands is highly promising, since these molecules are known to form highly stable complexes with interesting physical properties with transition-metal ions. A large number of different structures have been designed for many different applications, but polymers based on the application of coordinative forces have been prepared in a few cases only. Furthermore, the synthetic procedures applied frequently resulted in low yields. During the last few years, strong efforts have been made in the direction of self-assembling and supramolecular polymers as novel materials with "intelligent" and tunable properties. In this review, an overview of this active area at the interface of supramolecular and macromolecular chemistry is given.

The cover picture shows the molecular modeling of a star-shaped metallo-supramolecular polymer and the schematic drawing of a linear analogue. These molecules are of great interest because of their unique properties. Metallo-supramolecular polymers emerge by the well-directed combination of polymers, the properties of which have dominated the development of materials in recent years, with supramolecular ligands, which have the ability to organize spontaneously and form unique structures on a molecular level, and transition-metal ions, which, through their physical properties bring characteristic functionalities. The well-known properties of the individual components allow the use of established methods, such as UV/Vis spectroscopy, NMR spectroscopy, and gel permeation chromatography for characterization. However, the combination also requires the application of new methods, such as analytical ultracentrifugation or MALDI-TOF mass spectrometry. More about metallo-supramolecular polymers based on bipyridine and terpyridine complexes can be found in the review by U. S. Schubert and C. Eschbaumer on p. 2892 ff.

Single‐molecule force spectroscopy has been used for the investigation of the rupture behavior of individual metallo‐supramolecular systems. For this purpose, a specifically designed unsymmetrical α,ω‐functionalized poly(ethylene oxide) has been employed for mono‐termination with a terpyridine ligand and subsequently for the attachment onto atomic force microscopy (AFM) tips and microscope slide substrates. Metallo‐supramolecular complexes were formed by the use of ruthenium(III)–ruthenium(II) chemistry. Vertical stretching with the AFM cantilever ruptured the coordinative bonds. The rupture force of individual bisterpyridine ruthenium(II) complexes was determined to be 95 pN at a force loading rate of 1 nN s–1. Simultaneous rupturing of multiple parallel metallo‐supramolecular bonds was also observed. Monte Carlo simulations corroborated the experimental observations. The presented results lay the basis for the application of such metallo‐supramolecular systems in advanced functional nanomaterials.

No abstract

No abstract

Various mono- and disubstituted 2,2'-bipyridines were synthesized in high yields and multigram scales utilizing Stille-type coupling procedures. The corresponding bromo-picoline and tributyltin-picoline building blocks were prepared from commercially available amino-picoline compounds. As first examples of metal complexes, 4,5'-dimethyl-2,2'-bipyridine was reacted with copper(II) and iron(II) ions and investigated as catalyst in ATRP.

No abstract

No abstract