Time-resolved EPR spectra of a photoexcited phenanthrene-linked copper(II)-free-base porphyrin dimer: An intermediate-coupling case in a triplet-doublet spin system

Time-resolved electron paramagnetic resonance (TREPR) spectra are presented for a phenanthrene-linked copper(II)-free-base porphyrin dimer. In the lowest electronic excited state, the free-base half is in the (π, π*) triplet state and the copper-porphyrin half is in the doublet ground state due to the copper(II) spin. Because of the interaction between the triplet and doublet spins, the excited state of the dimer is described as a coupled triplet-doublet pair state. By choosing the excitation wavelength, this coupled state is produced via either the intersystem crossing within the free base or the energy transfer from the excited state of the copper porphyrin. The observed TREPR spectra show very large spectral widths compared to that of the triplet state in the free-base monomer. In addition, there is a prominent absorptive band in the center of the spectra regardless of the generation pathway. These features can be interpreted as characteristic properties in an intermediate-coupling case, where the degree of the triplet and doublet mixing largely depends on the molecular orientation relative to the magnetic field.