Modulator-Directed Counterintuitive Catenation Control for Crafting Highly Porous and Robust Metal–Organic Frameworks with Record High SO2 Uptake Capacity

Sulfur dioxide (SO2) is an important industrial feedstock that can be directly utilized or catalytically transformed to value-added chemicals such as sulfuric acid. The development of regenerable porous sorbents for the highly efficient storage and energy-minimal release of toxic SO2 operating under ambient conditions has attracted growing interest. Herein, we report the topology-guided construction of highly porous acs-type metal–organic frameworks (MOFs) through a counterintuitive modulator-directed catenation control approach. In contrast to the conventional modulator facilitated coordination competition that favors the thermodynamic catenated phase, we show that the elevation of modulator concentration can promote the formation of the noncatenated phase probably through a sublattice dissolution pathway. The assembly of a custom-designed trigonal prismatic triptycene-quinoxaline linker and trinuclear Fe3O cluster affords either the threefold catenated SJTU-219 or noncatenated SJTU-220 with desired acs net. Impressively, the synthetic approach is applicable to various metal ions, including Al3+, V3+, and even Ti4+. The noncatenated SJTU-220 exhibits an extraordinary SO2 sorption capacity of 29.6 mmol g–1 at 298 K and 1 bar, surpassing all reported solid sorbents. The uptake capacity can be further raised to 35.6 mmol g–1 via the replacement of Fe3+ with kinetically more inert Cr3+, resulting in a staggering ∼329-fold volume reduction compared with free ideal SO2 gas. Computational simulations suggest that unique Fe3+···S(SO2) interactions dominate the SO2 seeding process, facilitating the efficient packing of SO2 molecules in the large channels. Besides, the exceptionally low uptake at the low pressure region implies global weak framework-SO2 interactions, which offer great potential for practically implementing an “easy-on/easy-off” SO2 delivery system.