Singlet−Triplet Gap in Triplet Ground-State Biradicals Is Modulated by Substituent Effects

Three S = 1 bis(semiquinone) complexes have been prepared. To ensure ferromagnetic intramolecular exchange coupling, the two semiquinones are attached 1,3 to a 5-substituted phenylene ring. The biradical complexes differ in their meta-substituents: 1-NMe2, X = N,N-dimethylamino; 1-t-Bu, X = tert-butyl; 1-NO2, X = nitro. All three structures have been determined by X-ray crystallography. Results of structural studies indicate that the biradical ligands of all three complexes have nearly identical conformations with average semiquinone ring torsions of 32° ± 2° relative to the 5-substituted phenylene ring. The exchange parameter, J (Η = −2JŜ1·Ŝ2), ranges from +31.0 ± 0.6 cm-1 for 1-NO2 to +59.3 ± 1.2 cm-1 for 1-t-Bu, with J = +34.9 ± 0.7 cm-1 for 1-NMe2. Since the conformations are nearly identical, the differences in exchange coupling parameter J are due to substituent effects. The experimental results are supported by Hückel theory arguments and previous computational work.