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Theoretical study of the benzoquinone–tetrathiafulvalene–benzoquinone triad in neutral and oxidized/reduced states

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Abstract

This work presents a thorough DFT quantum-chemical characterization of the structural and electronic properties of the benzoquinone–tetrathiafulvalene–benzoquinone (Q–TTF–Q) triad in its neutral and oxidized/reduced states. The minimum-energy structure of the triad in its neutral state corresponds to a C 2v boat conformation, although the planar D 2h structure is also found to be a minimum-energy structure practically degenerate with the boat conformation. Upon oxidation, electrons are mainly extracted from the TTF backbone and the boat-shaped TTF structure evolves toward a planar D 2h and to a twisted D 2 conformation in the cation and dication, respectively. The theoretical characterization of the triad in its radical anion and dianion states is performed with several hybrid (B3LYP, PBE0 and BHHLYP), meta-hybrid (M06-2X) and long-range-corrected (CAM-B3LYP, ωB97X and ωB97XD) functionals. In gas phase, BHHLYP, M06-2X, CAM-B3LYP, ωB97X and ωB97XD functionals correctly predict the localized Q−–TTF–Q structure as the most stable structure, whereas the hybrid B3LYP and PBE0 functionals lead to a delocalized (Q–TTF–Q)− structure. The incorporation of solvent effects is crucial to provide a qualitatively correct description of the anion species where the localized solutions are found to be minimum-energy structures for all the functionals evaluated. The (Q–TTF–Q)2− dianion is predicted to be a biradicaloid species in its electronic ground state. Calculations predict that both Q− → Q0 and TTF → Q0 charge-transfer electronic transitions are associated with the low-energy, broad absorption band experimentally observed for the localized Q−–TTF–Q anion.

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Acknowledgments

This work has been supported by the Spanish Ministry of Economy and Competitiveness (MINECO) (CTQ2009-08790, CTQ2012-31914 and Consolider-Ingenio CSD2007-00010) and the Generalitat Valenciana (PROMETEO/2012/053).

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Authors and Affiliations

  1. Instituto de Ciencia Molecular, Universidad de Valencia, 46980, Paterna, Spain

    Joaquín Calbo, Juan Aragó & Enrique Ortí

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  1. Joaquín Calbo
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  2. Juan Aragó
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  3. Enrique Ortí
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Correspondence to Enrique Ortí.

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Published as part of the special collection of articles derived from the 8th Congress on Electronic Structure: Principles and Applications (ESPA 2012).

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Calbo, J., Aragó, J. & Ortí, E. Theoretical study of the benzoquinone–tetrathiafulvalene–benzoquinone triad in neutral and oxidized/reduced states. Theor Chem Acc 132, 1330 (2013). https://doi.org/10.1007/s00214-013-1330-3

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