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Intramolecular ferromagnetic coupling in bis-oxoverdazyl and bis-thioxoverdazyl diradicals with polyacene spacers

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Abstract

We predict the intramolecular exchange coupling constant (J) for 10 different oxo- and thioxo-verdazyl-based hi-spin ground-state diradicals with linear polyacene couplers of varying length using the broken symmetry approach in an unrestricted DFT framework. The magnetic characteristics of these systems are explained using the spin-density distribution, and an analysis is made by “magnetic” orbitals. The nuclear independent chemical shift (NICS) values have been calculated for the diradicals. The average NICS(1) (1 Å above the ring surface) value per benzenoid ring increases as the size of the coupler increases. So-called ΔNICS(1) values [the difference among average NICS(1) per benzenoid ring in the coupler and the NICS(1) of the linear polyacene molecule] are correlated with J values. Bond orders and hyperfine coupling constants have also been evaluated and analyzed for the diradicals.

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Acknowledgments

Financial support from Department of Science and Technology, India is thankfully acknowledged. S. Shil is thankful to UGC, India, for a fellowship. DJK acknowledges support (through grant BD-0894) from the Welch Foundation of Houston, Texas.

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Authors and Affiliations

  1. Department of Chemistry, University of North Bengal, Darjeeling, 734013, West Bengal, India

    Debojit Bhattacharya, Suranjan Shil & Anirban Misra

  2. MARS, Texas A&M University at Galveston, Galveston, TX, 77553, USA

    D. J. Klein

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  1. Debojit Bhattacharya
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  2. Suranjan Shil
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  3. Anirban Misra
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Correspondence to Anirban Misra.

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Bhattacharya, D., Shil, S., Misra, A. et al. Intramolecular ferromagnetic coupling in bis-oxoverdazyl and bis-thioxoverdazyl diradicals with polyacene spacers. Theor Chem Acc 127, 57–67 (2010). https://doi.org/10.1007/s00214-009-0705-y

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