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Download PDF by Katsuhiro Otomo: Akira Vol. 1, No. 3

By Katsuhiro Otomo

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Extra info for Akira Vol. 1, No. 3

Example text

The main differences between formed bonds are displayed in long-range action. 9. o ::l ~ ~ 2 ~ ::l CIJ E:. 0H 0, (NHCOR) OCOR NHCOR OH}I-" EHZ OH O. 10. ;. 1 Main Structural Principles 27 cule-molecule) can interact in long-range electrostatically and in more near distance approximately as the sum of covalent radii caused by covalent or coordinative bond formation. The total complex binding energy (combination of electrostatic and donor-acceptor) increases with increasing particle contact. The detailed investigation of all thermodynamic and kinetic regularities allows revelation of all reaction peculiarities as well as the structure of the formed polymer complexes.

The ,B-relaxation processes are practically independent of the metal content. In summary, it can be established that a correct evaluation of all terms of the polymer effect in thermodynamic description of complex formation with poly ligands is difficult. More important in this connection are conformational, electrostatic, concentration-dependent (different local concentration of functional groups), and supramolecular (macromolecule association and aggregation during complex formation) effects. 6 Main Transformations of Macroligands and Transition Metal Compounds During Complex Formation Both reacting components, macroligand of an organic polymer and MXn , often (practically every time) suffer different transformations during type I MMC formation.

The more noteworthy changes proceed in the period of identity of the macromolecule. It is composed of four monomer units instead of seven for the uncomplexed polymer. Structural studies show [50] that MMC properties in PEG-alkali metal ion complexes are better described in terms of the double-helix model. Other examples are: changes in the structure of po1yethers by interaction with transition metal halides [51], conformational transformations of po1y(2-vinylpyridine) during the 40 2 Synthesis and Structure of Macromolecular Metal Complexes complex formation with Co(AcAc)2 [52], conformational modifications of linear poly(amidoamines) caused by their protonation and complex formation [53], etc.

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Akira Vol. 1, No. 3 by Katsuhiro Otomo


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