Self-assembling molecular wires of halogen-bridged platinum complexes in organic media. Mesoscopic supramolecular assemblies consisting of a mixed valent Pt(II)/Pt(IV) complex and anionic amphiphiles

Nobuo Kimizuka, Noriko Oda, Toyoki Kunitake

研究成果: ジャーナルへの寄稿記事

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A novel class of supramolecular assemblies in organic media consisting of a molecular wire of a halogen-bridged platinum complex [Pt(en)2][PtCl2(en)2]4+ (en = 1,2 -diaminoethane) and anionic amphiphiles is developed. When double-chained phosphates or sulfonates are employed, the resultant [Pt(en)2][PtCl2(en)2]4+ - lipid complexes displayed intervalence charge transfer (CT) absorption bands in the crystalline state. They are soluble in organic solvents because of the amphiphilic superstructure, in which the solvophobic one-dimensional platinum complex is surrounded by solvophilic alkyl chains. CT absorption bands of halogen-bridged linear complexes are maintained in organic media, with varied colors that depend on the chemical structure of constituent amphiphiles. Monoalkylated phosphates failed to form colored, halogen-bridged ternary complexes probably because of their coordination to the axial position of Pt(II)(en)2. Formation of mesoscopic supramolecular assemblies in organic media was confirmed for the [Pt(en)2][PtCl2(en)2] complexes by electron microscopy. Interestingly, a supramolecular complex consisting of dihexadecyl sulfosuccinate and [Pt(en)2][PtCl2(en)2]4+ displayed clear, indigo solutions that are distinct from the yellow color observed for those of [Pt(en)2][PtCl2(en)2]/dialkyl phosphate complexes. The indigo color of the former complex disappeared upon heating the solution to 60 °C, whereas it reappeared reversibly by cooling the solution to room temperature. In electron microscopy, rodlike nanostructures with a minimum width of 18 nm and lengths of 700 - 1700 nm were observed after cooling, though not at elevated temperatures. Apparently, the lipid - [Pt(en)2][PtCl2(en)2]4+ complex undergoes reversible dissociation and reassembly processes in chloroform, and it becomes better dispersed after the reassembling process. The present finding opens a general route to solution chemistry of low-dimensional inorganic complexes and enables rational design and control of self-assembling inorganic molecular wires.

元の言語英語
ページ(範囲)2684-2689
ページ数6
ジャーナルInorganic chemistry
39
発行部数12
DOI
出版物ステータス出版済み - 6 12 2000

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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