Visualizing supramolecular assembly behavior, stimulus response, and solid state emission of higher-order Pt²⁺ aggregates

Here, we present the first instance of a highly efficient red tetramer aggregate with tunable emission based on a cationic platinum(II) complex in conjunction with a silver cluster anion counterpart. This system exhibits multicolor emission response behaviors, which can be conveniently and directly detected through spectroscopic analysis, showcasing intriguing luminescence changes. The self-assembly of Pt⋯, π-π, and hydrogen bonding interactions not only enables an intriguing color adjustment from green to yellow emission, and eventually to red emission, but also demonstrates the co-existence of the monomer, excimer, and aggregation. These phenomena are further accompanied by well-defined nanostructures. The self-assembly process of these structures exhibits an isodesmic growth mechanism, which is dependent on temperature. In this regard, it exhibits potential applicability in multi-mode logic gates that rely on external stimuli such as concentration, solvent, and temperature. The sensitivity of the aggregates towards chemical stimuli combined with their exceptionally bright emission characteristics renders them suitable for diverse applications including solid-state lighting sensing mechanisms and anticounterfeiting measures. The multi-stimuli responsive phosphorescence and self-assembly behaviors of the cationic platinum(II) complex were substantiated by X-ray crystal structure determination, ¹H NMR analysis spectroscopic investigations, computational calculations and scanning electron microscopy (SEM) studies.