Abstract
Abstract EPR spectra have been obtained for four spin-labeled bidentate ligands coordinated to manganese bis(hexafluoroacetylacetonate). Values of the electron-electron exchange coupling constants, J, were obtained in fluid solution. For two complexes with J ∼ 0, the frozen solution spectra of the nitroxyl signal showed well-resolved dipolar splitting by the Mn(II). The interspin distances were 9.0 and 9.7 A. The observation of resolved spin-spin splitting indicated that the manganese relaxation rate (T1−1) was slow compared with the magnitude of the splitting in hertz. This result contradicts a fundamental assumption of a widely used model of manganese-nitroxyl interaction. For two complexes with nonzero values of J there were no transitions that could be identified as nitroxyl transitions. This is attributed to extensive mixing of the nitroxyl and manganese wavefunctions.
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