Enhanced Intersystem Crossing, Yet Still Fluorescence Upon Introduction of Intermediate Charge-Transfer States in Hemicaged [Zn(bpy)₃]²⁺

Photoactive zinc(II) complexes typically undergo fluorescence from the singlet excited state as the dominant radiative pathway, as the operative spin–orbit coupling is usually very small and phosphorescence from the triplet state is strongly forbidden. Although dicationic zinc(II) tris(bipyridine) strictly follows this scheme with fluorescence at λem = 326 nm, constructing the ligand sphere as a hemicage was reported to lead to quantitative intersystem crossing (ISC) and subsequent fast phosphorescence with λem = 485 and a short radiative lifetime of ca. 1 μs. Surprised by this finding, we reinvestigated [Zn(bpy)3]2+ and its hemicage derivative in great detail, including variable temperature and time-resolved photophysical measurements in solution and solid state as well as high-level theoretical calculations to resolve their excited state behavior. Our investigations suggest that both compounds undergo fluorescence at room temperature with significantly different radiative rate constants of kr = 2 × 108 and 1.2 × 106 s–1, respectively, and only weak phosphorescence on the millisecond time scale at low temperatures. The major difference is the occurrence of additional charge-transfer states within the ligand scaffold of the hemicage, which accelerate the ISC to the 3LC(bpy) state from 350 s down to 82 ns and reduce the fluorescence rate constant.