Pore Environment Optimization of Microporous Metal-Organic Frameworks with Huddled Pyrazine Pillars for C₂H₂/CO₂...

Metal-organic frameworks (MOFs) have been proven promising in addressing many critical issues related to gas separation and purification. However, it remains a great challenge to optimize the pore environment of MOFs for purification of specific gas mixtures. Herein, we report the rational construction of three isostructural microporous MOFs with the 4,4',4"-tricarboxyltriphenylamine (H₃TCA) ligand, unusual hexaprismane Ni₆O₆ cluster, and functionalized pyrazine pillars [PYZ-x, x = -H (DZU-10), -NH₂ (DZU-11), and -OH (DZU-12)], where the building blocks of Ni₆O₆ clusters and huddled pyrazine pillars are reported in porous MOFs for the first time. These building blocks have enabled the resulting materials to exhibit good chemical stability and variable pore chemistry, which thus contribute to distinct performances toward C₂H₂/CO₂ separation. Both single-component isotherms and dynamic column breakthrough experiments demonstrate that DZU-11 with the PYZ-NH₂ pillar outperforms its hydrogen and hydroxy analogues. Density functional theory calculations reveal that the higher C₂H₂ affinity of DZU-11 over CO₂ is attributed to multiple electrostatic interactions between C₂H₂ and the framework, including strong C≡C···H-N (2.80 Å) interactions. This work highlights the potential of pore environment optimization to construct smart MOF adsorbents for some challenging gas separations.