Light and Heat-Driven Flexible Solid Supramolecular Polymer Displaying Phosphorescence and Reversible Photochromism

Herein, a type of light- and heat-driven flexible supramolecular polymer with reversibly long-lived phosphorescence and photochromism is constructed from acrylamide copolymers with 4-phenylpyridinium derivatives containing a cyano group (P-CN, P-oM, P-mM), sulfobutylether-beta-cyclodextrin (SBCD), and polyvinyl alcohol (PVA). Compared to their parent solid polymers, these flexible supramolecules based on the non-covalent cross-linking of copolymers, SBCD, and PVA efficiently boost the phosphorescence lifetimes (723.0 ms for P-CN, 623.0 ms for P-oM, 945.8 ms for P-mM) through electrostatic interaction and hydrogen bonds. The phosphorescence intensity/lifetime, showing excellent responsiveness to light and heat, sharply decreased after irradiation with a 275 nm flashlight or sunlight and gradually recovered through heating. This is accompanied by the occurrence and fading of visible photochromism, manifesting as dark green for P-CN and pink for P-oM and P-mM. These reversible photochromism and phosphorescence behaviors are mainly attributed to the generation and disappearance of organic radicals in the 4-phenylpyridinium derivatives with a cyano group, which can guide tunable luminescence and photochromism. A flexible supramolecule based on non-covalent cross-linking among acrylamide copolymers with 4-phenylpyridinum derivatives containing a cyano group, sulfobutylether-beta-cyclodextrin (SBCD) and polyvinyl alcohol (PVA) efficiently induces and boosts room-temperature phosphorescence and photochromism through electrostatic interaction and hydrogen bonds, showing excellent reversibility tuned by the generation and disappearance of organic radicals under UV-light and heat. image