Dispersion-Driven Conformational Isomerism in σ-Bonded Dimers of Larger Acenes

Authors

  • Dr. Stephan Ehrlich,

    1. Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie der Universität Bonn, Beringstrasse 4, 53115 Bonn (Germany)
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  • Prof. Dr. Holger F. Bettinger,

    1. Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen (Germany)
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  • Prof. Dr. Stefan Grimme

    Corresponding author
    1. Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie der Universität Bonn, Beringstrasse 4, 53115 Bonn (Germany)
    • Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie der Universität Bonn, Beringstrasse 4, 53115 Bonn (Germany)
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  • This work was supported by the DFG within the framework of the SFBs 858 and 813. The authors thank Dr. A. Hansen for help with the CEPA calculations.

Abstract

original image

The σ-bonded butterfly structure of the nonacene dimer shows unusual dispersion-driven conformational isomerism that is due to strong intramolecular dispersion interactions between the wings of annulated aromatic rings. High-level LPNO-CEPA and DFT-D3 ab initio calculations are in good mutual agreement, whereas dispersion-devoid DFT and the MP2 method completely fail.

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