Multinuclear macromolecule metal complexes 2. Preparation and characterization of Prussian blue and its analogs bonded to pofy(vinylamine hydrochloride) |
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| Authors: | T. Koyama R. Hayashi T. Yamane E. Masuda A. Kurose K. Hanabusa H. Shirai T. Hayakawa N. Hojo |
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| Affiliation: | (1) Present address: Department of Functional Polymer Science and Institute of High Polymer, Faculty of Textile Science and Technology, Shinshu University, Ueda, Japan;(2) Institute of High Polymer, Faculty of Textile Science and Technology, Shinshu University, Ueda, Japan;(3) Shinshu University, Matsumoto, Japan |
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| Abstract: | Prussian blue and its analogs bonded to poly(vinylamine hydrochloride) (PVAm · HCl) containing FeII or FeIII and M2+ (M=Fe, Co, Cu) in a 1 1 molar ratio were obtained by the reaction of [Fe(CN)6]n– (n=3,4) with M2+ ion-PVAm · HCl mixture in aqueous solution. Under a limited polymer concentration (TVAm/TFe over 10), these polymer complexes thus obtained were stable and soluble in water. By casting these solutions, colored films can be produced. The formation of Prussian blue and its analogs bonded to PVAm · HCl was also investigated by the Benesi-Hildebrand method. The molar extinction coefficients of intervalence charge transfer (FeII FeIII, CoIIFeIII, FeIICuII) band for MFe(CN)6](n–2)– bound to PVAm · HCl (M=Fe, Co, Cu) were found to be 10,100–9601 · mol–1 · cm–1 at 25  C. The formation constants were found to be in the range of 107 to 1010 M–1. The changes of enthalpy ( H) and entropy (S) were found to be in the range of –10.4 to –22.5 kJ · mol–1 and 5.7 to 52.9 J · K–1 mol–1 respectively, at 25C. |
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| Keywords: | Mixed valence complex Prussian blue analog intervalence charge transfer polyion complex |
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