Polarity-Tunable Luminescence and Intersystem Crossing of a Zinc(II) Diimine Dithiolate Complex

Combined density functional theory and multireference configuration interaction methods including spin-orbit interactions have been employed to investigate the photophysical properties and deactivation pathways of a zinc diimine dithiolate complex involving the phenanthroline derivative bathocuproine and the dianionic dithiosquarate as chelating ligands. Zn(batho)(dtsq) is one of the few luminescent zinc complexes for which triplet emission had been reported in the solid state [Gronlund, P. Inorg. Chim. Acta 1995, 234, 13-18]. Because of the high dipole moment of the complex in the electronic ground state, ligand-to-ligand charge-transfer (LLCT) states experience strong hypsochromic shifts in polar media, while ligand-centered (LC) states are nearly unaffected. Rate constants for the thermally activated upconversion of the T_LLCT population to the S_LLCT state are promising due to a small singlet-triplet energy gap and the participation of the sulfur in the electronic excitation, but the T_LLCT state is not the lowest-lying excited triplet state in ethanol solution. In addition to the T_LLCT electronic structure, T_LC(batho)^' and T_LC(dtsq) ππ* excitations form minima on the T₁ potential energy surface. The S_LLCT luminescence is expected to be quenched at the nanosecond time scale by the dark T_LC(dtsq)ππ* state. Moreover, a T_LC(dtsq)σπ* state has been identified, which leads to degradation of the compound. In mildly polar media, the dark triplet LC states are energetically inaccessible and the lowest excited singlet and triplet states clearly exhibit an LLCT character. However, their mutual spin-orbit coupling is reduced to the extent that reverse intersystem crossing is not very likely at room temperature. While Zn(diimine)(dithiolate) complexes continue to be perceived as an interesting substance class with potential application as emitters in electroluminescent devices, the particular Zn(batho)(dtsq) complex is not considered suitable for that purpose.