@article{oai:gifu-pu.repo.nii.ac.jp:00012164,
 author = {奥村, 典子 and オクムラ, ノリコ and OKUMURA, Noriko},
 journal = {岐阜藥科大學紀要, The annual proceedings of Gifu College of Pharmacy},
 month = {Jun},
 note = {P(論文), 有機化合物のπ電子系ダイアニオンは,中性分子のLUMOへの二電子添加により生成し,母体化合物とは著しく異なる物理化学的性質に起因する特異的な分子認識が期待される。本研究では,電気化学的および分光学的手法を用いて有機πダイアニオンの分子認識に伴うn-o型およびπ-π型電荷移動錯体生成能を評価し,その特徴を分子軌道理論を基に明らかにした。そして,π電子系ダイアニオンの特異的な分子認識は,錯体生成に対するフロンティア軌道の変化に起因するものであり,同時にこれらの分子認識能は電気化学的に制御可能であることが示された。, Charge-transfer (CT) complex formation based on molecular recognition of organic π-dianions has been investigated by electrochemistry and spectroelectrochemistry combined with ab initio MO calculations. The p-quinone dianions (PQ^<2->) form the 1 : 2 hydrogen-bonded complexes with MeOH at low concentrations of MeOH, and the 1 : 4 complexes at high concentrations. The hydrogen bonding of PQ^<2-> with MeOH is characterized by the geometrical and spectral properties. It was demonstrated that this situation is due to the strong n-σCT interaction in the hydrogen bonds. The results suggest that the differing functions and properties of biological quinones are conferred by the n-σCT interaction through hydrogen bonding of the dianions with their protein environment. On the other hand, it has been demonstrated that π-dianions of redox-active organic molecules, such as chloranil (CL) and tetracyanoethylene (TCNE), form the π-π type CT complexes with 4nπ biphenylene (BP), caused by the favorable intermolecular HOMO-LUMO interaction. Spectroelectrochemistry evidently gave the intermolecular CT spectra in the CL^<2->-BP and TCNE^<2->-BP systems. These systems involving the bistable CT complex formation, modulated by redox reactions of CL and TCNE, are characterized by the geometrical properties and the trichromic change.},
 pages = {13--24},
 title = {<総説>有機π電子系ダイアニオンの分子認識に基づく分子化合物生成に関する研究},
 volume = {50},
 year = {2001}
}