Studies on Hydrophobic Association of Metal Complexes and on Structures and Properties of Oil-like State

1.通过x射线衍射和电导率测量，发现[M (en)(phen)]^<2+> （M=Pt或Pd）配合物与1-萘乙酸离子之间存在强离子缔合关系。在上述金属配合物的存在下，1,10-菲罗啉（phen）或2,2'-联吡啶（bpy）对水的溶解度显著提高。通过x射线衍射测量[M (en)(phen)]^<2+>和phen溶解水溶液的径向分布函数，发现了几个间隔为3.5Å的周期峰，表明存在由配合物和phen分子的芳环叠加形成的层状结构的超分子。发现了一种特殊的现象，即[M (phen)_3]^<3+>或[M (bpy)_3]^<3+> （M=三价金属）的萘磺酸盐水溶液（1-NS或2-NS）在一定的组成范围内被分离成稀、浓两种液相。它们的相图与苯酚-水体系相图相似，具有临界溶解温度（T_c），超过该温度相分离现象消失。phen配合物的T_c明显大于bpy配合物，1-NS盐的T_c略大于2-NS盐。通过对[M (bpy)_3] (1-NS)_3浓水溶液的x射线衍射测量发现，配合物在溶液中聚集，部分1-NS^-芳香环渗透到配合物的疏水孔中，溶液结构几乎不受温度的影响。当衍射强度在较低角度增加时，在具有相分离成分的溶液中观察到由于水分子局部化而引起的密度波动。

1.Strong ion association was observed between [M (en)(phen)]^<2+> (M=Pt or Pd) complexes and 1-naphthaleneacetate ions by X-ray diffraction and conductivity measurements.2.The solubility of 1,10-phenanthroline (phen) or 2,2'-bipyridine (bpy) for water was remarkably increased in the presence of the above metal complexes.3.Radial distribution functions obtained by X-ray diffraction measurements of aqueous solutions dissolving [M (en)(phen)]^<2+> and phen revealed several periodic peaks having 3.5Å intervals, suggestine the existence of supramolecules having the layer structure formed by the stacking of aromatic rings of the complex and phen molecules.4.A saecific ahenomenon was found that an aqueous solution of naphthalenesulfonate (1-NS or 2-NS) of [M (phen)_3]^<3+> or [M (bpy)_3]^<3+> (M=trivalent metal) was separated into two liquid phases of dilute and concentrated solutions in a given composition range. Their phase diagrams, similar to that of the phenol-water system, had the critical solution temperature (T_c) above which the phase-separation phenomenon disappeared. The T_c for the phen complex was significantly larger than that for the bpy complex, and the T_c for the 1-NS salt was somewhat larger than that for the 2-NS salt.5.From X-ray diffraction measurements of concentrated aqueous solutions of [M (bpy)_3] (1-NS)_3 it was found that complexes were aggregated in solutions, a part of aromatic rings of 1-NS^- penetrated into the hydrophobic pockets of the complexes, and the solution structure was almost independent of temperature. Density fluctuations due to the localization of water molecules were observed in solutions having compositions just before the phase separation as the diffraction intensity increased at lower angles.