Dye-Encapsulated Zeolitic Imidazolate Framework (ZIF-71) for Fluorochromic Sensing of Pressure, Temperature, and Volatile Solvents.

Abstract

Luminescent metal-organic frameworks (MOFs) offer a multifunctional platform for creating noninvasive sensors and tunable optoelectronics. However, fluorochromic materials that are photophysically resilient and show high sensitivity toward different physical and chemical stimuli are scarce. We report a facile host-guest nanoconfinement strategy to construct a fluorescent hybrid material with multiple sensing capabilities. We design and fabricate a new Guest@MOF material: comprising a zeolitic MOF (ZIF-71) as a nanoporous host for encapsulating rhodamine B (RhB dye) guest molecules, resulting in an RhB@ZIF-71 system with mechanochromic, thermochromic, and solvatochromic sensing response. The fluorochromic sensing properties stem from the nanoconfinement effect that ZIF-71 imposes on RhB monomers, yielding the H- or J-type aggregates with tunable photophysical and photochemical properties. For mechanochromism, the external pressure causes an emission red shift in a linear fashion, switching RhB guests from H-type to J-type aggregates through a shear deformation. For thermochromism, we demonstrate a linear scaling as a function of temperature due to the spatial restriction imposed on J-type aggregates incarcerated in ZIF-71 pores. Harnessing the solvatochromism of RhB@ZIF-71, we interrogated its photochemical response by employing three diverse groups of volatile organic compounds. The multimodal sensing response paved the way to smart applications like photonic pressure sensors, noninvasive thermometers, and ultrasensitive chemosensors.