Very Strongly Ferromagnetically Coupled Diradicals from Mixed Radical Centers: Nitronyl Nitroxide Coupled to Oxoverdazyl via Polyene Spacers

Abstract

We predict extremely large and positive intramolecular magnetic exchange coupling constants (J) for coupled diradicals constructed from nitronyl nitroxide (NN) and oxoverdazyl (o-VER). These radicals have the general formula o-VER(N)-nC-NN where nC represents an olefinic spacer with n = 0, 2, 4, 6, and 8. Species like o-VER(C)-nC-NN have negative coupling constants. The atoms in the parentheses show the point of attachment of the coupler to the verdazyl moiety. Both the N-linked series and C-linked series have comparable stability. The triplet molecular geometries were optimized by the density functional (UB3LYP) method using the 6-311 g(d,p) basis set. This was followed by single-point UB3LYP calculations using 6-311++g(3df,3pd) basis. To calculate J, single-point broken-symmetry computations were performed on the optimized triplet geometries and using the same basis set. The N-linked diradicals coupled through conjugated polyenes are topologically different. These are found to have coupling constants of the order of 1000 cm(-1), whereas the C-linked diradicals show coupling constants of the order of -100 cm(-1). In general, for both cases, the absolute magnitude of the coupling constant decreases with the increase in the length of the spacer.