Luminescence properties and relaxation processes of strongly correlated organic radical TTTA crystals and molecules

Photoluminescence of strongly correlated organic radical 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) crystals was measured at room temperature in order to elucidate the relaxation process in the excited state, which is responsible for an initiation of the photoinduced magnetic phase transition in this material. The electronic structure and luminescence properties of TTTA molecule were also investigated to clarify the relaxation process. We found that a luminescence band lies at 1.8 eV in the high-temperature (HT) phase crystal having almost same characteristics as that in TTTA molecule, suggesting that the intramolecular lattice distortion plays an important role for the relaxation process. On the other hand, a broad luminescence band appears at 1.4 eV with a large Stokes shift in the low-temperature (LT) phase crystal. The large Stokes shift observed shows that rearrangement of the dimerized TTTA molecules toward the evenly spaced radicals takes place due to a large intermolecular lattice distortion. This molecular rearrangement in the excited state initiates the photoinduced magnetic phase transition from the LT to HT phases in this material.