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Long, multicenter bonding in π-[terthiophene] 2+2 dimers

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Abstract

The repulsive nature of the interaction between the cation radicals of the π-[terthiophene] 2+2 dimers, 1 2+ 2 , found in crystals has been concluded from B3LYP/6-31+G(d) calculations. Hence, the bonding component is weaker than the Coulombic repulsion, consistent to recent findings for [TTF]·+–[TTF]·+ interactions (TTF = tetrathiafulvalene). The existence of 1 2+ 2 dimers originates from the cation+–anion− electrostatic interactions, which exceeds the combined effect of the 1 .+–1 .+ plus (SbF6)−–(SbF6)− repulsions in 1 2(SbF6)2, similar to what is found for [TTF]·+–[TTF]·+ interactions in [TTF]2(ClO4)2 aggregates and in crystals. The long, multicenter bond in 1 2+ 2 is characterized as a 2e−/10c bond from an Atoms-in-molecules analysis.

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Notes

  1. B3LYP is a density functional obtained by taking the three parameter non-local exchange functional of Becke and the non-local correlation functional of Lee-Yang-Parr [22, 23].

  2. The MCQDPT/CASSCF(2,2) method performs multiconfigurational perturbation calculation on a multiconfigurational CASSCF(2,2) wavefunction using the MCQDPT method [24] provides an accurate evaluation of the dispersion component of the interaction energy and gives results similar to those obtained using the more popular CASPT2 method [25]. The (2,2) active space in these CASSCF(2,2), and MCQDPT/CASSCF(2,2) calculations was that resulting from combining the two SOMO orbitals of the fragments.

  3. The validity of the counterpoise method for correcting the BSSE was demonstrated analytically in Ref. [29] and numerically in Ref. [30].

  4. The closed-shell singlet state of the [TTF]2(ClO4)2 aggregate was also found to be −19.7 kcal/mol more stable than its fragmentation into two [TTF]+ and two (ClO4)− ions at the crystal geometry (the open-shell singlet and triplet states are also more stable than the fragments by −19.6 and −6.8 kcal/mol, respectively).

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Acknowledgments

I.G. Yoldi and J.J. Novoa were supported by the Spanish Science and Education Ministry (BQU2002-04587-C02-02 and UNBA05-33-001, and Ph.D. grant to I.G. Yoldi) and the CIRIT (2001SGR-0044 and 2005-PEIR-0051/69). Computer time was also provided by CESCA and BSC. J.S. Miller was supported in part by the U. S. NSF (Grant No. 0553573), and the DOE (Grant No. DE FG 03-93ER45504). One of us would also express here his gratitude to Prof. S. Olivella for his guidance, support, and personal friendship in the early years of his scientific career.

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Authors and Affiliations

  1. Departament de Química Física and IQTCUB Facultat de Química, Universitat de Barcelona, Av. Diagonal, 647, 08028, Barcelona, Spain

    Iñigo Garcia Yoldi & Juan J. Novoa

  2. Department of Chemistry, University of Utah, Salt Lake City, UT, 84112-0850, USA

    Joel S. Miller

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  1. Iñigo Garcia Yoldi
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  2. Joel S. Miller
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  3. Juan J. Novoa
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Correspondence to Joel S. Miller or Juan J. Novoa.

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Dedicated to Professor Santiago Olivella on the occasion of his 65th birthday and published as part of the Olivella Festschrift Issue.

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Yoldi, I.G., Miller, J.S. & Novoa, J.J. Long, multicenter bonding in π-[terthiophene] 2+2 dimers. Theor Chem Acc 123, 137–143 (2009). https://doi.org/10.1007/s00214-009-0543-y

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