Light-Gating Crystalline Porous Covalent Organic Frameworks

We report light gating in synthetic one-dimensional nanochannels of stable crystalline porous covalent organic frameworks. The frameworks consist of 2D hexagonal skeletons that are extended over the x–y plane and stacked along the z-direction to create dense yet aligned 1D mesoporous channels. The pores are designed to be photoadaptable by covalently integrating tetrafluoro-substituted azobenzene units onto edges, which protrude from walls and offer light-gating machinery confined in the channels. The implanted tetrafluoroazobenzene units are thermally stable yet highly sensitive to visible light to induce photoisomerization between the E and Z forms. Remarkably, photoisomerization induces drastic changes in intrapore polarity as well as pore shape and size, which exert profound effects on the molecular adsorption of a broad spectrum of compounds, ranging from inorganic iodine to organic dyes, drugs, and enzymes. Unexpectedly, the systems respond rapidly to visible lights to gate the molecular release of drugs and enzymes. Photoadaptable covalent organic frameworks with reversibly convertible pores offer a platform for constructing light-gating porous materials and tailorable delivery systems, remotely controlled by visible lights.