Pressure‐Modulated Luminescence Enhancement and Quenching in a Hydrogen‐Bonded Organic Framework

Light emission in the solid state is central for illumination, sensing, and imaging applications. Unlike luminescence in dilute solutions, where the excited states are unimolecular in nature, intermolecular interaction plays a significant role in the quantum yield of solid-state luminophores, manifested as competing aggregation-caused quenching (ACQ) and aggregation-induced enhancement (AIE). Both effects are extensively studied in various systems; however, it remains unclear how their competition depends on molecular conformation and intermolecular stacking. Here the direct observation of pressure-modulated AIE-ACQ competition in a crystalline hydrogen-bonded organic framework (HOF) is reported. Using in situ spectroscopies and computational modeling, the intramolecular vibration and intermolecular π-π stacking directly responsible for the non-radiative decay of the excited state are identified. The extent of these two contributions is modulated by hydrostatic pressure and guest molecules in the HOF pores. This work demonstrates a physically neat model system to understand and control solid-state luminescence, and a potential material platform for piezoluminescent sensing.