A Porous Crystalline Nitrone‐Linked Covalent Organic Framework

Herein, we report the synthesis of a nitrone‐linked covalent organic framework, COF‐115, by combining N, N′, N′, N′′′‐(ethene‐1, 1, 2, 2‐tetrayltetrakis(benzene‐4, 1‐diyl))tetrakis(hydroxylamine) and terephthaladehyde via a polycondensation reaction. The formation of the nitrone functionality was confirmed by solid‐state 13C multi cross‐polarization magic angle spinning NMR spectroscopy of the 13C‐isotope‐labeled COF‐115 and Fourier‐transform infrared spectroscopy. The permanent porosity of COF‐115 was evaluated through low‐pressure N2, CO2, and H2 sorption experiments. Water vapor and carbon dioxide sorption analysis of COF‐115 and the isoreticular imine‐linked COF indicated a superior potential of N‐oxide‐based porous materials for atmospheric water harvesting and CO2 capture applications. Density functional theory calculations provided valuable insights into the difference between the adsorption properties of these COFs. Lastly, photoinduced rearrangement of COF‐115 to the associated amide‐linked material was successfully demonstrated. A nitrone‐linked covalent organic framework, COF‐115, has been synthesized for the first time via polycondensation reaction. The sorption analyses of COF‐115 revealed a porosity of 1387 m2/g, and a superior potential for atmospheric water harvesting and CO2 capture applications compared to their imine‐based analogs. Finally, COF‐115 was found to undergo a photochemical rearrangement to the corresponding amide‐linked material.