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

金属配合物的疏水缔合及类油态结构与性能的研究

• 批准号: 10440197
• 负责人: YOKOYAMA Haruhiuko
• 金额: $ 8.58万
• 依托单位: YOKOHAMA CITY UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10440197/
• 关键词: oil-like state; phase separation; stacking; hvdrophobic interaction; supramolecule; metal complex; phenanthroline; solution X-ray diffraction; 二相分離; 臨界共溶温度; 錯体; ビピリジン; 疎水性会合; 積層構造; 白金錯体; パラジウム錯体; X線回折; 溶液構造

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.

1.通过X-射线衍射法和电导法测定了[M(En)(Phen)]~(2+)&gt；(M=铂或钯)与1-萘乙酸根离子之间的离子缔合作用。2.1，10-邻菲咯啉(Phen)和2，2‘-联吡啶(Bpy)在水中的溶解度显著增加。4.发现了一种特殊的现象，即[M(Phen)_3]或[M(Bpy)_3]或[M(Bpy)_3]或[M(Bpy)_3]^&lt；3+&gt；[M(Å)_3]或[M(Bpy)_3]^&lt；3+&gt；(M=三价金属)的1-NS或2-NS水溶液在给定的组成范围内被分成稀液和浓液两种液体。它们的相图与苯酚-水体系的相图相似，有一个临界溶解温度(T_C)，超过这个温度相分离现象消失。[M(Bpy)_3](1-NS)_3浓水溶液的T_c明显大于bpy络合物的T_c，1-NS盐的T_c略大于2-NS盐的T_c。对[M(Bpy)_3](1-NS)_3浓水溶液的X-射线衍射仪测定发现，络合物在溶液中聚集，部分1-NS~-芳环穿透到络合物的疏水口袋中，溶液结构与温度无关。在相分离前，由于水分子的局域化而引起的密度波动随着衍射强度在较低角度的增加而被观察到。

项目成果

横山晴彦: "迅速溶液X線回折装置を用いたX線回折実験法とデータ処理法"横浜市立大学論叢 自然科学系列. 52巻(印刷中). (2001)

Haruhiko Yokoyama：“使用快速溶液X射线衍射仪的实验X射线衍射方法和数据处理方法”横滨市立大学系列自然科学系列第52卷（出版中）。

K.Kanno, H.Yokoyama, and Y.Yoshimura: "A New Interpretation of Anomalous Properties of Water Based on Stillinger's Postulate."J.Phys.Chem.B. Vol.105, No.10. 2019-2026 (2001)

K.Kanno、H.Yokoyama 和 Y.Yoshimura：“基于斯蒂林格假设的水异常性质的新解释。”J.Phys.Chem.B。

Kazutaka Kondo: "Conductivity and Solvation of Li^+ Ions of LiPF_6 in Propylene Carbonate Solutions"J.Phys.Chem.B. (in press).

Kazutaka Kondo：“碳酸丙烯酯溶液中 LiPF_6 的 Li^ 离子的电导率和溶剂化”J.Phys.Chem.B。

Yuri,Mizuno: "Effects of Tripositive Cobalt(III)-Complex Ions on the Structure of a Cholesteric Mesophase Composed of Potassium N-Dodecanoyl-L-alaninate" Langmuir. 14・24. 7058-7064 (1998)

Yuri，Mizuno：“三正钴（III）络合物离子对 N-十二酰基-L-丙氨酸钾组成的胆甾型中间相结构的影响”Langmuir 14・24（1998）。

Kazutaka Kondo: "Conductivity and Solvation of Li^+ Ions of LiPF_6 in Propylene Carbonate Solutions"J.Phys.Chem.B. 104. 5040-5044 (2000)

Kazutaka Kondo：“碳酸丙烯酯溶液中 LiPF_6 的 Li^ 离子的电导率和溶剂化”J.Phys.Chem.B。