A linker extension strategy for generating metal− organic frameworks (MOFs) with superior moisture-capturing properties is presented. Applying this design approach involving experiment and computation results in MOF-LA2-1 {[Al(OH)-(PZVDC)], where PZVDC 2− is (E)-5-(2-carboxylatovinyl)-1Hpyrazole-3-carboxylate}, which exhibits an approximately 50% water capacity increase compared to the state-of-the-art water-harvesting material MOF-303. The power of this approach is the increase in pore volume while retaining the ability of the MOF to harvest water in arid environments under long-term uptake and release cycling, as well as affording a reduction in regeneration heat and temperature. Density functional theory calculations and Monte Carlo simulations give detailed insight pertaining to framework structure, water interactions within its pores, and the resulting water sorption isotherm.

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.

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.