Guest-Induced Gate-opening in a Flexible MOF Adsorbent That Exhibits Benzene/Cyclohexane Selectivity

IF 6.1 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Inorganic Chemistry Frontiers Pub Date : 2025-03-10 DOI:10.1039/d5qi00261c

Guo-Ao Li, Ming Deng, Wei Guo, Shuang Yin, Yan-E Liu, Ai-Xin Zhu, Michael Zaworotko

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Abstract

We report the synthesis of a 2-fold interpenetrated primitive cubic (pcu) topology network, X-pcu-11-Zn, formulated as [Zn₂(DMTDC)₂(dpb)] (H₂DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid; dpb = 1,4-di(pyridin-4-yl)benzene). Upon removal of solvent from the as-synthesised form, X-pcu-11-Zn-, transformation from a large-pore “open” phase to a narrow pore phase, X-pcu-11-Zn-, occurred. The -phase subsequently exhibited guest-induced switching as evidenced by a 2-step type F-IV2 adsorption isotherm for N₂ at 77 K and a 3-step profile with two gate-opening pressures for CO₂ at 195 K. Dynamic vapour sorption studies revealed selective sorption of methanol, ethanol, and CH₃CN over H₂O at 298 K. Further, X-pcu-11-Zn- selectively adsorbed benzene over cyclohexane concomitant with a gate-opening effect driven by structural transformations. Importantly, the transformations between the guest-free and guest-loaded structures were found to be reversible over six adsorption/desorption cycles. Single-crystal X-ray diffraction analysis of the Bz loaded phase indicates that selective benzene binding can be attributed to π-π and C-H···π aromatic packing interactions.

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