ORD and CD studies of poly[(S)(−)-N-α-methylbenzylethylenimine] |
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Authors: | AD Aliev EP Tiurina AYu Koschevnik SL Alieva BA Krentsel |
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Institution: | Institute of Petrochemical Synthesis, USSR Academy of Sciences, Moscow, U.S.S.R. |
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Abstract: | The advantages of chiral N-substituted polyethylenimines for the chiroptical study of macromolecular conformations in solution have been considered. Poly(S)(?)-N-α-methylbenzylethylenimine] (poly-3) and five model compounds have been obtained and their chiroptical properties studied. The cyclic dimer and tetramer of imine 3 are suitable models for the chiroptical study of configurational and conformational behaviour of randomly coiled and helical poly-3 in solution. Unlike the disordered poly-3 in acidified solvents and the configurational models in various solvents, helical poly-3 in hydrocarbon solvents has positive optical rotation and positive CD-band of the tertiary amine chromophore at 223 nm. The appearance of this inherently chiral chromophore of the helix explains the observed changes of the sign and values of the optical rotation of poly-3 in various solvents which are mainly caused by conformational transformations of the main chain. The presence of helical conformations of poly-3 in solution are also confirmed by optical rotation data of stereocopolymers and the concentration dependence data of ORD curves of poly-3. This conclusion agrees with NMR and i.r.-data. |
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