Selective Stabilization of the Spin States of a Magnetically Anisotropic Dysprosium Ion Induced by Photo-Excitation of the Associated Cyclic π-Conjugated System.

ABSTRACT

The presence of a new electronic interaction, which couples a 4 f-electronic system with a total angular momentum J and a photoexcited cyclic π-conjugated system with an orbital angular momentum L, in the bis(phthalocyaninato)dysprosium single-molecule magnet ([DyPc2 ]- ) is reported. Two π-π* excited states in the visible spectral region of the [DyPc2 ]- complex, which are denoted here as QL and QH , showed significantly different temperature and field dependences of the magnetic circular dichroism (MCD) A-term intensity. This phenomenon not only indicates the presence of a "J-L" interaction, but also that the interaction generates two different preferred orientations of the J-L pair, either parallel (for the QH band) or antiparallel (for the QL band), depending on the excitation energy. We have constructed a theoretical model that reproduces the temperature and field dependences, and quantitatively evaluated the J-L interaction.