Cyclometalated Iridium(III) Schiff Base Complexes for Chemiluminogenic Bioprobes

Abstract Chemiluminogenic bioimaging has emerged as a promising paradigm due to its independence from light excitation, thereby circumventing challenges related to light penetration depth and background autofluorescence. However, the availability of effective chemiluminophores remains limited, which substantially impedes their bio‐applications. Herein, we discovered for the first time that cyclometalated iridium(III) Schiff base complexes can unexpectedly generate chemiluminescence. Notably, the chemiluminescence reaction was rapid, with a half‐life of only 0.86 s, significantly faster than previously reported examples. Unlike conventional chemiluminescent scaffolds, the distinguishing feature of the chemiluminogenic iridium(III) complex is its unique intramolecular imine‐to‐amide conversion upon reaction with reactive oxygen species (ROS). Intriguingly, the chemiluminogenicity of these complexes is not influenced by the cyclometalating ligands but is closely associated with the Schiff base ligand, allowing for tuning of the emission colors via altering the cyclometalating ligands. Additionally, we formulated one of the Schiff base complexes ( 1 ) as water‐soluble chemiluminogenic nanoparticles (CLNPs) and successfully employed them as activatable chemiluminescence bioprobes for precise and rapid imaging of hypochlorite‐related biological events both in vitro and in vivo . We believe that this significant finding of the development of chemiluminogenic Schiff base complexes will greatly facilitate the designing of innovative chemiluminophores for theranostic applications.