| Project/Area Number |
13650929
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
高分子合成
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
KANBARA Takaki Tokyo Institute of Technology, Chemical Resources Laboratory, Associate Professor, 資源化学研究所, 助教授 (90204809)
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| Co-Investigator(Kenkyū-buntansha) |
KITANO Hiromi Toyama University, Faculty of Engineering, Professor, 工学部, 教授 (40115829)
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| Project Period (FY) |
2001 – 2002
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| Project Status |
Completed (Fiscal Year 2002)
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| Budget Amount *help |
¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2002: ¥800,000 (Direct Cost: ¥800,000)
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| Keywords | Macrocycles / Thioamide / Aminopyridine / Cyclic ligand / Metal complex / Inclusion compound / Self-assembly / Thin film / 芳香族アミン |
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| Research Abstract |
We have prepared new macrocyclic ligands, azacalixpyridines, by Pd-catalyzed aryl amination. The macrocyclic ligands have nitrogen lone pair electrons and offer donor site in the cavity. We have attempted complexation of zinc and copper ions with the macrocycles, and the obtained inclusion complexes were characterized by NMR spectroscopy and X-ray crystallography.
Thiocarbonylation of a macrocyclic tetralactam also gave a new macrocyclic polythiolactam. The chemical transformation enhanced hydrogen-bonding ability of the N-H protons in the cavity, and provided strong affinity toward anions. The association properties of the polythiolactam with anions was examined by ^1H NMR titration. The molecular structures of the macrocyclic host compound and its Cl^- complex were determined by X-ray structural analysis.
The polythiolactam has four thiocarbonyl groups which are located on the outside of the cavity. We have attempted formation of self-assembled monolayer (SAM) of the polythiolactam on the gold electrode. Cyclic voltammograms of the polythiolactam modified electrodes indicated formation of a covalent sulfur-metal bond and well packed monolayer on the gold electrode. The covalent sulfur-metal bond formation was also supported by surface enhanced raman spectroscopy (SERS). The model transition-metal camplexes constituted of thioamide-based tridentate ligands have been prepared and their molecular structures were determined by x-ray structural analysis.
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