Zn-Based Metal-Organic Frameworks Using Triptycene Hexacarboxylate Ligands: Synthesis, Structure, and Gas-Sorption Properties

Chemistry. 2023 Nov 16;29(64):e202302080. doi: 10.1002/chem.202302080. Epub 2023 Oct 12.

Abstract

A series of metal-organic frameworks (MOFs) based on zinc ions and two triptycene ligands of different size have been synthesized under solvothermal conditions. Structural analyses revealed that they are isostructural 3D-network MOFs. The high porosity and thermal stability of these MOFs can be attributed to the highly rigid triptycene-based ligands. Their BET specific surface areas depend on the size of the triptycene ligands. In contrast to these surface-area data, the H2 and CO2 adsorption of these MOFs is larger for MOFs with small pores. Consequently, we introduced functional groups to the bridge-head position of the triptycene ligands and investigated their effect on the gas-sorption properties. The results unveiled the role of the functional groups in the specific CO2 binding via an induced interaction between adsorbates and the functional groups. Excellent H2 and CO2 properties in these MOFs were achieved in the absence of open metal sites.

Keywords: X-ray crystallographic analysis; gas adsorption; gas storage; metal-organic frameworks; porous coordination polymers; structural analysis; substituent effect; triptycene.