Coordination Self‐Assembly Induced Hot Exciton Fluorescence and Multi‐Source Excitation Long Afterglow

Metal-organic complexes with long afterglow luminescence have attracted extensive attention due to potential applications in display, sensing and information security. However, most of the metal-organic complex long afterglow materials reported so far are limited to the use of UV light as the excitation source, and the ambiguity of the structure-activity relationship makes the development of metal-organic complexes extremely limited. Herein, a series of metal-organic complexes with ultralong emission lifetime is constructed by coordination assembly of Zn(II) with three isomers. These complexes can emit afterglow when excited by UV light, blue LED, cell phone flashlight or even near-infrared light (800 nm) under ambient conditions, and the afterglow is also observed at 360 K. More interestingly, the inactivation pathway of the triplet exciton was altered by the strategy of supramolecular self-assembly, which leads to these complexes having hot exciton fluorescence (HEF) emission that is not present in the ligand. The relationship between structure and optical properties is investigated in detail by experiments and theoretical calculations. This work provides guidance for studying the modulation of optical properties by coordination interactions.