Spin−Spin Interactions in Porphyrin-Based Monoverdazyl Radical Hybrid Spin Systems

The spin−spin interactions in a complex consisting of a metalloporphyrin with a verdazyl radical attached at one of the β positions of the porphyrin ring are investigated. The X-ray crystal structure of the copper porphyrin complex shows that the plane of the verdazyl moiety is oriented such that it is nearly perpendicular to the plane of the porphyrin ring so that weak magnetic interactions between the metal and radical are expected. Consistent with this expectation, magnetic susceptibility and continuous-wave electron paramagnetic resonance (EPR) measurements of the copper (d9) and vanadyl (d1) versions of the porphyrin show that the metal and radical are weakly antiferromagnetically coupled. Thus, the ground state is a singlet, but the triplet state is thermally accessible above ∼5 K. Spin-polarized transient EPR measurements of the free-base analogue show that its lowest excited state is a quartet, indicating that the verdazyl radical couples ferromagnetically to the triplet excited state of the porphyrin. Low-temperature transient EPR measurements on the vanadyl porphyrin reveal that the lowest excited quintet state is populated. This implies that the antiferromagnetic coupling between the metal and radical observed in the ground state is switched to a ferromagnetic arrangement in the excited state by the presence of the unpaired electrons in the π and π* orbitals of the porphyrin.