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本文测定了八种电子受体与十五种电子给体间的电荷转移(CT)光谱.利用文献中根据极谱还原电位求得之受体的亲合势,论证了同一电子给体与各种电子受体相作用时,其CT光谱也符合Mulliken公式;公式中的C为变化不大的数,可近似地认为是常数.本文还用电子吸收光谱首次研究了同系列电子受体(TCNE,n=0,2,3,4)与六种电子给体的CT配合作用,实验表明其CT吸收光谱也近似地服从同系线性规律;随着同系序数的增加,CT光谱发生紫移,而不象同系列给体与同一受体作用那样发生红移.用差示脉冲极谱法测定了此受体系列的还原峰电位,求得其电子亲合势;并用EHMO法计算了它们的前线分子轨道的能量.结果表明,随着同系序数的增加,亲合势减小,最低空轨道能量升高,从而解释了CT光谱紫移现象.
In this paper, the charge-transfer (CT) spectra between eight electron acceptors and fifteen electron donors were determined. By using the acceptor affinity obtained from the polarographic reduction potential in the literature, The electron spectrum of the electron acceptor is also consistent with the Mulliken formula, and C in the formula is a small number that can be approximated as a constant. In this paper, the electron acceptor spectra of the same series of electron acceptors (TCNE , n = 0, 2, 3, and 4) and CTs of six kinds of electron donors. The experimental results show that their CT absorption spectra also approximate to the homologous linear law. With the increase of homologous series number, Not like the same donor donor and the same redox shift occurred.Using differential pulse polarography to measure the reduction peak potentials of this acceptor series, to obtain its electron affinity; and using EHMO method to calculate their front line Molecular orbital energy.The results show that with the increase of homologous series number, the affinity decreases and the energy of the lowest empty orbit increases, which explains the phenomenon of purple shift of CT spectrum.