Boosting Luminescence of Planar‐Fluorophore‐Tagged Metal–Organic Cages Via Weak Supramolecular Interactions

Abstract A variety of planar organic fluorophores (R=phenyl, naphthalenyl, pyrenyl) and luminescence promotors (X=Cl, Br, I) were equipped, respectively, on the alternatively arranged vertices of cubic Zn II ‐imidazolate cages through orthogonal subcomponent self‐assembly. It was found that supramolecular interactions, especially weak C−H⋅⋅⋅X interactions, play a key role in activating an efficient radiative pathway, coupled with reduced nonradiative decay rate through metal coordination, therefore significantly boosting the emission quantum yields of the system. This finding provides a strategy that utilizes molecular geometry and supramolecular interactions to modulate the emission efficiency of luminescent cage‐based materials.