Zinc(II) Complexes with Triplet Charge-Transfer Excited States Enabling Energy-Transfer Catalysis, Photoinduced Electron Transfer, and Upconversion.

Many Cu complexes have luminescent triplet charge-transfer excited states with diverse applications in photophysics and photochemistry, but for isoelectronic Zn compounds, this behavior is much less common, and they typically only show ligand-based fluorescence from singlet π-π* states. We report two closely related tetrahedral Zn compounds, in which intersystem crossing occurs with appreciable quantum yields and leads to the population of triplet excited states with intraligand charge-transfer (ILCT) character. In addition to showing fluorescence from their initially excited ILCT states, these new compounds therefore undergo triplet-triplet energy transfer (TTET) from their ILCT states and consequently can act as sensitizers for photo-isomerization reactions and triplet-triplet annihilation upconversion from the blue to the ultraviolet spectral range. The photoactive ILCT state furthermore facilitates photoinduced electron transfer. Collectively, our findings demonstrate that mononuclear Zn compounds with photophysical and photochemical properties reminiscent of well-known Cu complexes are accessible with suitable ligands and that they are potentially amenable to many different applications. Our insights seem relevant in the greater context of obtaining photoactive compounds based on abundant transition metals, complementing well-known precious-metal-based luminophores and photosensitizers.