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INSIGHTS INTO THE SOLVATO-/THERMO-PROMOTED INTRAMOLECULAR ELECTRON TRANSFER IN A TTF-sigma -TCNQ DYAD WITH AN EXTREMELY LOW HOMO-LUMO GAP

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INSIGHTS INTO THE SOLVATO-THERMO-PROMOTED INTRAMOLECULAR ELECTRON TRANSFER IN A TTF-sigma -TCNQ DYAD WITH AN EXTREMELY LOW HOMO-LUMO GAP.htm (411bytes)
Date
2012-06
Author
Zhou, Yuhua
Tan, Kai
谭凯
Lu, Xin
吕鑫
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  • 化学化工-已发表论文 [14469]
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Abstract
The low-lying states of an organic donor-sigma-acceptor dyad, i.e. tetrathiafulvalene-sigma-tetracyano-p-quinodimethane (TTF-sigma-TCNQ), in gas phase and in various solvents have been investigated by means of hybrid DFT calculations in combination with the conductor-like polarizable continuum model to describe solvent effects. It has been shown that the dyad, though preferring a closed-shell singlet ground state with an eclipsed conformation in gas phase, adopts the charge-separated zwitterionic states with an extended conformation (TTF+-sigma-TCNQ(-)), i.e. open-shell singlet biradical ground state immediately followed by triplet biradical state, in polar solvent (CH3CN and CH2Cl2) as a result of the intramolecular electron transfer (ET) stimulated by solvent polarization. The degree of such intramolecular ET is so strongly dependent on the polarity (dielectric constant) of solvent that the zwitterionic biradical states become more stable with respect to the closed-shell singlet state with increasing polarity of the solvent. As such, the dyad should show a higher ratio of biradicals in more polar solvent and/or at higher temperature and, hence, is chameleonic in nature.
Citation
JOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY,2011,11(3):599-609
URI
http://dx.doi.org/10.1142/S0219633612500393
WOS:000305540600010
https://dspace.xmu.edu.cn/handle/2288/15356

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