Development of New Field of Solution Coordination Chemistry from a Viewpoint of Precursor Phenomena for "Supramolecular Effect

1. 对于双核配合物[VO(sakenO)]_2(CH_2)_n（n=3,6,10,12）与Fe（III）之间的氧化还原反应速率，随着n的增加，激活焓和熵增加，并在该体系中观察到互补效应。在乙腈中，氧桥式Ru（III）双核配合物对（III，II）和（II，II）的还原电位通过质子给体或BF3的加入而向正电（ca.1V）移动，并且这种移动和相关电子数受质子给体pKa值的控制。对[M(en)_3]^<3+>, [M(chxn)_3]^<3+>, [M(phen)_3]^3（M=Co^<III>, Cr^<III>）与胶束的相互作用用^<59>Co核磁共振（Co^<III>）和^<13>C顺磁弛豫（Cr^<III>）进行了考察，表明与磺酸离子或硫酸盐离子和羧酸盐的相互作用程度反映了选择性。讨论了FT拉曼光谱在溶液配位化学中应用的可能性和局限性。利用顺磁性Cr（III）配合物的^2H NMR谱研究了溶液状态下螯合环构象的溶剂效应和温度依赖性。这些问题与第二协调领域的弱相互作用有关。研究了高浓度电解质中溶剂与离子的协同作用和水溶液中疏水离子的缔合作用，以及胶束中络合物的形成。这些研究将有望在介观现象方面取得进展。

1. For redox reaction rates between dinuclear complexes [VO(sakenO)]_2(CH_2)_n(n=3,6,10,12) and Fe(III), the activation enthalpy and entropy increases with increasing n, and the complimentary effect is observed in this system.2. The reduction potentials from oxo-bridged Ru(III) dinuclear complexes to (III,II) and (II,II) in acetonitrile are found to shift to positive (ca.1V) by addition of proton donor or BF3, and this shift and the numbers of electrons concerned are controlled by the pKa values of the proton donors.3. The examination of the interaction of [M(en)_3]^<3+>, [M(chxn)_3]^<3+>, [M(phen)_3]^3(M=Co^<III>, Cr^<III>) with the micelles in terms of ^<59>Co NMR(Co^<III>) and ^<13>C paramagnetic relaxation (Cr^<III>) demonstrates that the extent of the interactions with sulphonic or sulfate ions and carboxylates reflects the selectivity.4. The possibility and limitation of application for FT Raman spectroscopy to solution coordination chemistry was discussed. The dynamics of chelate ring conformation in solution state was investigated with respect to the solvent effect and temperature dependence by ^2H NMR spectra of paramagnetic Cr(III) complexes. These subjects were discussed in relation with weak interactions in the second coordination sphere.5. The cooperative interaction between solvents and ions in highly concentrated electrolytes and hydrophobic ion association in aqueous solutions were investigated together with the complex formation in micelles. These studies will be expected to progress in connection with the mesoscopic phenomena.