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

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 A 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.