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Computational insights into the electronic structure of TCNDQ and TCNP: the effect of Si substitution

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Abstract

Tetracyanodiphenoquinodimethane (TCNDQ) and tetracyanopyrenoquinodimethane (TCNP) are larger cyanocarbons related to tetracyanoethylene (TCNE) and tetracyanoquinodimethane (TCNQ). In contrast to TCNE and TCNQ, there are limited studies detailing the electronic structure of TCNDQ and TCNP. In this work, we provide structural characterization and adiabatic electron affinities (AEAs) of TCNDQ and TCNP. The isovalent substitution strategy (swapping C for Si) discussed previously by our group is applied, and the effect of Si substitution on the potential energy surfaces and AEAs of the parent compounds is assessed. Si substitution enhances the AEAs and stabilizes the triplet diradical ground state of both compounds. These findings provide missing information regarding the electronic structure of TCNDQ and TCNP and further demonstrate the effectiveness of the isovalent substitution strategy.

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Notes

  1. The deviation in calculated ESR constants is available in SI-Tables 13 and 14

  2. Imaginary frequencies could not be removed in these cases. They lead back to the twisted D2 structure described

  3. M06-L increases in the order BS4 < BS1 < BS2 < BS3

  4. The DIA Values are computed as the difference between the average double bond DI and average single bond DI. This is done so that DIA carries the same sign as BLA

  5. M06/BS2 is CS symmetry but displays no pyramidalization

  6. Further attempts to calculate the energy of the OSS by using the triplet wavefunction and permuting the orbitals resulted in the CSS solution being obtained.

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Acknowledgements

The authors would like to thank SHARCNET and Compute Canada for computational resources.

Funding

SMM was supported by a grant through Indigenous and Northern Affairs Canada (INAC) Post-Secondary Student Support Program. Finally, the authors was supported by Lakehead University and the Natural Sciences and Engineering Research Council (NSERC).

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  1. Department of Chemistry, Lakehead University, Thunder Bay, ON, Canada

    Steven M. Maley & Robert C Mawhinney

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  1. Steven M. Maley
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  2. Robert C Mawhinney
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Correspondence to Robert C Mawhinney.

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Maley, S.M., Mawhinney, R.C. Computational insights into the electronic structure of TCNDQ and TCNP: the effect of Si substitution. Struct Chem 30, 1873–1885 (2019). https://doi.org/10.1007/s11224-018-1265-3

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