Intrachain charge-transfer complex in ethanol solution on a polysarcosine chain having a terminal electron donor and a terminal electron acceptor groups.

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概要

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• Polysarcosine having a terminal electron donating group (<I>p</I>-dimethylaminoanilide group) and a terminal electron accepting group (3,5-dinitrobenzoyl group) was synthesized. An ethanol solution of the polymer showed a distinct charge-transfer absorption band around 435 nm. With use of the extinction coefficient determined for the low-molecular-weight model compounds, the fraction of polymers forming an intrachain complex was evaluated to be about 0.08 for \bar<I>n</I>=6 (\bar<I>n</I> is the degree of polymerization of the polysarcosine chain). The fraction decreased with rise in temperature and increase in chain length. The fraction experimentally observed was considerably larger than that estimated from the Monte Carlo calculation on polysarcosine chain, indicating that the cyclic conformations are greatly stabilized by the intrachain charge-transfer interaction. Thermodynamic parameters were determined for the intrachain complex. The chain length dependence of the parameters in ethanol was the opposite of that obtained previously in a chloroform solution. The difference was explained in terms of the difference of the conformations of polysarcosine chain in chloroform and in ethanol solutions. This was evidenced by the NMR spectra recorded in the solvents.

• 公益社団法人 日本化学会の論文

著者

• Sisido Masahiko

  Department Of Bioengineering Science Faculty Of Engineering Okayama University

• Takagi Hiroaki

  Department Of Food Science And Technology Faculty Of Agriculture Nagoya University:(present Address)

• Imanishi Yukio

  Department Of Material Chemistry Graduate School Of Engineering Kyoto Univeresity

• Higashimura Toshinobu

  Department Of Materials Science School Of Engineering The University Of Shiga Prefecture

• Takagi Hiroaki

  Department of Polymer Chemistry, Kyoto University

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