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Bis-dibenzo[a.i]fluorenylidene, does it exist as stable 1,2-diradical?

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Abstract

The geometries, energies, and electronic properties of the two possible configurations of bis-[dibenzo[a.i]fluorenylidene] were investigated theoretically by density functional theory DFT B3LYP at the UB3LYP/6-311 + G(2d,p) // UB3LYP/6-31 + G(d,p) level of theory. According to the performed calculations, it was found that the singlet is 3.4 kcal mol-1 lower in energy compared to triplet state at room temperature. This gap is compared with those of other alkenes like ethylene, (61.9 kcal mol-1) tetra-tert-butyethylene, (6.4 kcal mol-1) and bis-fluorenylidene (19.5 kcal mol-1). These results confirm the experimental findings of the paramagnetic properties determined by Franzen and Joschek. The low singlet-triplet gap in the case of bis-[dibenzo[a.i]fluorenylidene] is the result of a steric destabilization of the singlet due to strain and stabilization of the triplet electronic state by delocalization of each free electron within each aromatic moiety. This correlates with the special electronic structure of the triplet state of this compound, where facial interaction of two hydrogen atoms lying close to the lobes of each p-orbital occupied with a single electron at the distorted double bond in the triplet electronic state.

a) The singlet form of bis-dibenzo[a.i]fluorenylidene. b) The triplet form of bis-dibenzo[a.i]fluorenylidene. The central dihedral angle around the C=C double bond changes from 53.2° in the singlet electronic structure to 90.0° in the triplet electronic structure. Of great interest is the very low singlet-triplet gap of this electronic system which equals to 3.4 kcal/mol according to calculation by DFT UB3LYP/6-311+G(2d,p) // UB3LYP/6-31+G(d,p) level of theory.

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Acknowledgments

We thank Dr. Kurt Polborn for his valuable comments on the x-ray structural data of compound 3. We thank Professor Yitzhak Apeloig for his helpful comments.

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Authors and Affiliations

  1. Research Unit Analytical Biogeochemistry, Helmholtz Zentrum München, Ingolstädter Landstr.1, 85758, Neuherberg, Germany

    Basem Kanawati, Philippe Schmitt-Kopplin & Dieter Lenoir

  2. Department Chemie and Catalysis Research Center, Technische Universität München, 85747, Garching, Germany

    Alexander Genest

  3. Technische Universität München, Lehrstuhl für Analytische Lebensmittelchemie/Chair of Analytical Food Chemistry, Alte Akademie 10, 85354, Freising, Germany

    Philippe Schmitt-Kopplin

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  1. Basem Kanawati
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  2. Alexander Genest
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Correspondence to Basem Kanawati or Dieter Lenoir.

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Kanawati, B., Genest, A., Schmitt-Kopplin, P. et al. Bis-dibenzo[a.i]fluorenylidene, does it exist as stable 1,2-diradical?. J Mol Model 18, 5089–5095 (2012). https://doi.org/10.1007/s00894-012-1502-4

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