Structural and functional expansion of metal–organic frameworks (MOFs) is fundamentally important because it not only enriches the structural chemistry of MOFs but also facilitates the full exploration of their application potentials. In this work, by employing a dual-site functionalization strategy to lock the ligand conformation, we designed and synthesized a pair of biphenyl tricarboxylate ligands bearing dimethyl and dimethoxy groups and fabricated their corresponding framework compounds through coordination with copper(II) ions. Compared to the monofunctionalized version, introduction of two side groups can significantly fix the ligand conformation, and as a result, the dual-methoxy compound exhibited a different network structure from the mono-methoxy counterpart. Although only one almost orthogonal conformation was observed for the two ligands, their coordination framework compounds displayed distinct topological structures probably due to different solvothermal conditions. Significantly, with a hierarchical cage-type structure and good hydrostability, the dimethyl compound exhibited promising practical application value for industrially important C2H2 separation and purification, which was comprehensively demonstrated by equilibrium/dynamic adsorption measurements and the corresponding Clausius–Clapeyron/IAST/DFT theoretical analyses.
The exploration of reticular chemistry pertaining to rod-packing metal–organic frameworks and the development of solid adsorbents for multitask hydrocarbon separations are two active topics of current research. In this study, an In-organic coordination framework compound denoted ZJNU-121 was assembled from a custom-designed bithiophene-functionalized tetracarboxylate ligand. The title compound not only exhibited a rare two-way rod-packing pattern but also displayed the impressive capability of capturing C2 hydrocarbons from CH4 and CO2 to achieve C2/C1 and C2/CO2 separations. Under ambient conditions, the ideal adsorbed solution theory-predicted adsorption selectivities for equimolar mixtures fall in the range of 8.4–13.8 (C2H n /CH4) and 2.3–3.4 (C2H n /CO2). Such separation potentials were also ascertained by the column breakthrough experiments. Furthermore, the in-depth theoretical insight unveiled the crucial role of active sites such as thiophene sulfur, carboxylate oxygen, and the bridging μ2-OH group in capturing C2 hydrocarbons in preference to CO2 and CH4. Additionally, the structural integrity of ZJNU-121 can be retained in aqueous solutions with pH values varying from 3 to 11 for 24 h at ambient temperature, as verified by the preservation of PXRD patterns, textural characteristics, and static/dynamic adsorption behaviors. This research not only enriched the architectural diversity of rod MOFs but also reported a robust adsorbent with good application prospects for diversified hydrocarbon separations.
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