High-molecular-weight poly(ethylene oxide)s are utilized for a wide variety of different applications. Here we present a new strategy for the large-scale synthesis of modified metallosupramolecular poly(ethylene oxide)s on the basis of the metal-induced self-assembly of bis(2,2′:6′,2′′-terpyrid-4′-yl)-poly(ethylene oxide) 179. The influence of different metal ions (cadmium(II), copper(II), cobalt(II), nickel(II), iron(II)) on the degree of polymerization and the resulting molecular weight were evaluated. Elaborated reaction conditions allow easy access to high-molecular-weight iron(II) coordination polymers via self-organization. The polymers were characterized in detail utilizing 1 H NMR, UV/vis spectroscopy, MALDI-TOF-MS, and viscosity measurements. The molecular weight was estimated on the basis of concentration-dependent viscosity measurements to about 80 000 g/mol. Furthermore, the morphology of the utilized telechelic bis(2,2′:6′,2′′-terpyrid-4′-yl)-poly(ethylene oxide) 179 and the corresponding coordination polymer was investigated using atomic force microscopy. In particular, the influence of complex formation on the morphology was investigated.

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In the present contribution, we synthesized linear coordination polymers based on oligo(ethylene glycol)s as well as poly(ethylene glycol)s and terpyridine ruthenium(II) complexes. The reaction conditions, e.g., solvent, concentration, were varied to obtain well‐soluble, high molecular weight polymers. The resulting compounds were characterized by UV‐vis and NMR spectroscopy. The viscosity of the materials was also investigated with and without salt addition. Finally, the polymers were characterized with DSC and AFM. AFM revealed a lamellar morphology. magnified image

Access to supramolecular polymers: Large scale synthesis of 4′-chloro-2,2′ : 6′,2′′-terpyridine and an application to poly(propylene oxide) telechelics , Designed Monomers and Polymers, 5:2-3, 211-221To link to this article: http://dx.Abstract-A new improved large scale synthesis of 4 0 -chloro-2,2 0 : 6 0 ,2 00 -terpyridine is described in detail. Williamson type ether reactions were utilized for a high yield reaction of 4 0 -chloro-2,2 0 : 6 0 ,2 00 -terpyridine with ®;!-bishydroxy-functionalized poly(propylene oxide). The completeness of the functionalizationwas proven by NMR, GPC and MALDI-TOF-MS investigations. The application of ruthenium(III)/ (II) chemistry allowed then the construction of ABA type non-covalent architectures.

Starting in biochemistry and pharmaceutical chemistry, combinatorial methods, automated synthesis and high‐throughput characterization are being further developed for organic synthesis and polymer research. The development is strongly driven by the achievements in biochemistry and pharmaceutical chemistry and the need to minimize the time‐to‐market for novel polymeric products. The success of high‐throughput methodologies in polymer science is partially limited by the commercially available hardware (synthesizers, workstations, robots, online‐characterization instruments, etc.) and software. A short overview of commercially available equipment for polymer research is provided in this Review.magnified image

The well‐known reaction of 4′‐chloro‐2,2′:6′,2′′‐terpyridine with alkoxide nucleophiles leads to 4′‐functionalized 2,2′:6′,2′′‐terpyridines. This reaction allows the easy introduction of different functional groups onto the terpyridine at the 4′‐position, i.e. opposite to the metal binding site, in one reaction step. Among the functionalized 2,2′:6′,2′′‐terpyridines reported here are amines (including chiral examples), carboxylic acids, simple alkoxy‐chain terpyridines with different chain lengths, and a stilbene‐functionalized terpyridine. Moreover, the synthesis of two important already known substances was significantly improved. One example of a sequential functionalization of the (aminopentoxy)terpyridine with a dithiolane functionality is also reported. For two of the alkyl‐chain‐functionalized terpyridines, single‐crystal X‐ray crystallographic data were obtained. Finally, ordered monolayers of alkyl‐substituted terpyridines on HOPG were visualized using STM. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Here we demonstrate the synthesis of telechelics with different spacer units and different numbers of metal‐complexing units, like α‐methoxy‐ω‐(2,2′:6′,2″‐terpyrid‐4′‐yl)‐poly(ethylenoxide)78 (1), bis(2,2′:6′,2″‐terpyrid‐4′‐yl) di(ethylene glycol) (2), bis(2,2′:6′,2″‐terpyrid‐4′‐yl)‐poly(ethylene oxide)180 (3) and tris[(2,2′:6′,2″‐terpyrid‐4′‐yl)‐oligo (ethylenoxy‐)3.33]glycerin (4) utilizing 4‐chloro‐2,2′:6′,2″‐terpyridine. The complexation behaviour of a variety of metal‐salts towards the telechelics was studied and different supramolecular architectures were investigated, such as symmetric polymeric complexes and linear coordination polymers. Furthermore, attempts have been undertaken to prepare metallo‐supramolecular cross‐linked systems.

Summary: The success of automated and parallel drug‐discovery workflows in pharmaceutical research has sparked similar developments in materials science. This contribution provides an overview of published high‐throughput experimentation work in the area of polymeric coatings and thin films. Methodological aspects, experimental examples, and remaining challenges are discussed.Robotic system (GE) for crosshatch application.magnified imageRobotic system (GE) for crosshatch application.