The Ground State of Multispin Systems Based on Verdazyl and Nitrene Radicals: An EPR and Quantum-Chemical Study

In this study, low-temperature EPR spectroscopy and quantum-chemical techniques were employed to investigate multispin systems─1,5-diphenyl-3-(3-nitrenophenyl)-6-oxoverdazyl and 1,5-diphenyl-3-(4-nitrenophenyl)-6-oxoverdazyl─that contain a nitrene center at either a <i>meta</i>- or <i>para</i>-position, respectively. Ground states and magnetic zero-field splitting (ZFS) parameters of these multispin systems were determined by experimental and computational methods. The results indicated that the high-spin quartet state is a ground state, and the quartet-doublet energy gap is close to 10 kcal/mol for the <i>para</i>-position of the nitrene group, with ZFS parameters <i>D</i> = 0.292 cm^-1 and <i>E</i>/<i>D</i> = 0.002 cm^-1. In contrast, for the <i>meta</i>-position, the low-spin doublet state is favored with an energy gap of 1 kcal/mol. The observed difference in the ground states could be qualitatively explained by an analysis of the spin density distribution and by delocalization of the unpaired π-electron of the nitrene center. Overall, this study provides valuable insights into the electronic structures and magnetic parameters of such multispin systems.