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首页> 外文期刊>Russian Journal of Physical Chemistry >DonorAcceptor Interaction and Intramolecular Proton Transfer in Aminopolyenes
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DonorAcceptor Interaction and Intramolecular Proton Transfer in Aminopolyenes

机译：氨基多烯中的供体受体相互作用和分子内质子转移

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摘要

The influence of donor and acceptor substituents at chain termini on the geometry of the chain and charge distribution on atoms was studied for the ground and lower triplet electronically excited state of model Wdimethylaminopolyene molecules (CH3)2N(CH=CH)nCH=C(CN)2, n = 1–3. Calculations were performed by the B3LYP/6-31+G** method. The influence of substituents on bond lengths and the ampli tude of deviations from the equilibrium carbon–carbon bond length in unsubstituted polyenes increased as the conjugation chain grew longer. The deviations of the effects of both donor and acceptor groups from addi tivity, however, decreased. In the lower triplet electronically excited state of the molecule, the effect of sub stituents on changes in C–C bond lengths along the chain was not damped. The section of the potential energy surface for intramolecular proton shift from the donor amino to the acceptor nitrile group in “cyclic” (cis) conformers of the H2N–CH=CH–CN and H2NCH=CH–CH=CH–CN molecules was analyzed. The structure of the reaction transition state and the height of the barrier to proton transfer were calculated.
机译：研究了模型二甲基氨基多烯分子（CH3）2N（CH = CH）nCH = C（CN）的基态和较低三重态电子激发态，研究了链末端供体和受体取代基对链的几何形状和原子上电荷分布的影响。 ）2，n = 1-3。通过B3LYP / 6-31 + G **方法进行计算。随着共轭链的延长，取代基对键长的影响以及未取代多烯中平衡碳-碳键长的偏差的幅度也随之增加。然而，供体和受体组的作用与可加性的偏差减小了。在分子的三重态较低电子激发态下，取代基对沿着链的C–C键长变化的影响没有受到抑制。分析了H2N–CH = CH–CN和H2NCH = CH–CH = CH–CN分子的“环状”（顺式）构象的分子内质子从供体氨基转移至受体腈基的势能表面截面。计算了反应过渡态的结构和质子转移的势垒高度。

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