A novel synthetic concept is presented which allows, for the first time, the preparation of soluble, constitutionally well-defined transition-metal coordination polymers of considerable molecular weights from kinetically unstable, pseudotetrahedral copper(1)-and silver(1)-phenanthroline complexes. It is demonstrated that rigorous exclusion of all molecules that might act as competitive ligands for the metal ions of the polymer constitutes the central requirement for obtaining solutions of "proper" coordination polymers, i.e., polymers having a constant number of repeating units per individual chain. Tetrachloroethane was found to be an appropriate solvent for this purpose. Solubility of the copper(1) and silver(1) coordination polymers -which are polyelectrolytes -in this rather apolar solvent was achieved by the attachment of two hexyl side chains to each polymer repeating unit. It was thus possible to prove the defect-free constitution of the obtained coordination polymers and to show their excellent stability in solution with the aid of 'H and I3C NMR spectroscopy. Moreover, formation of coordination polymers of considerable chain lengths is supported by the complete disappearance of end-group absorptions in the 'H NMR spectra and the results of viscosimetric investigations.

Readily soluble copper(I) and silver(I) coordination polymers have been prepared via the conversion of equimolar amounts of p-phenyleneethynylenebridged bis [9-(p-anisyl) 6 or AgBF 4 as their metal-monomer counterparts. The homogeneous constitution of the resulting diamagnetic macromolecules is proven using NMR spectroscopy. Their average degrees of polymerization have been shown to reach values of P n ≥ 20, and the intrinsic viscosity of the resulting randomly coiled polyelectrolytes is of the order [η] ≈ 30 mL/g in 0.01 M NH 4 PF 6 /acetone. Moreover, NMR and viscosity experiments show the chain molecules to be open solution aggregates when dissolved in coordinating solvents like acetonitrile or water. When dissolved in noncoordinating solvents, on the other hand, the multinuclear complexes were found to be "true" polymers, i.e. macromolecules with a constant number of repeating units per individual chain with respect to time. At very high dilution, transformation of the high-molecular-weight chain molecules into cyclic oligomers is observed in coordinating solvents but not in non-coordinating media.

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The grafting reaction of methyl methacrylate onto polybutadiene (PB) was investigated with different chromatographic techniques, including high‐performance liquid chromatography (HPLC) and online coupled two‐dimensional liquid chromatography. As a result of the grafting reaction, a complex mixture of nongrafted PB, the graft copolymer PB‐g‐PMMA [where PMMA is poly(methyl methacrylate)], and the PMMA homopolymer was formed. The complete separation of all the products of the grafting reaction was achieved with gradient HPLC. By the combination of gradient HPLC and size exclusion chromatography in a fully automated two‐dimensional chromatography setup, the complex distributions of the chemical composition and molar mass were fingerprinted simultaneously. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3143–3148, 2003