Optical activity levels of metal centers controlling multi-mode emissions in low-dimensional hybrid metal halides for anti-counterfeiting and information encryption

Abstract

In-depth insight into the electronic competition principles between inorganic units and organic ligands proves to be extremely challenging for controlling multi-mode emissions in low-dimensional hybrid metal halides (LHMHs). Herein, an efficient blue emission from organic ligand was engineered in (DppyH)2MCl4 (Dppy = diphenyl-2-pyridylphosphine, M = Zn2+, Cd2+) due to the reverse type I band alignment constructed by optically inert units with nd10 shell electrons. By contrast, the optically active [MnCl4]2− with semi-fully filled 3d5 shell electrons prompts the band alignment of type II, resulting in the narrowband green emission of Mn2+, along with an energy transfer from DppyH+ to [MnCl4]2−. Beyond that, the band alignment of (DppyH)SbCl4 is further reversed to type I due to the strong stereochemical activity of 5s2 lone-pair electrons, resulting in the triplet-state (3P1 → 1S0) self-trapped exciton (STE) emission of [SbCl4]−. The conclusion is that the electronic configurations of metal centers govern the optical activity levels of inorganic units, which in turn controls the multi-mode emissions by maneuvering the band alignments. This research provides an enlightening perspective on the multi-mode emissions with tunable photoluminescence and resulting electronic transitions of LHMHs, whose derived emitters can be employed in anti-counterfeiting and information encryption.