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Mixed-Ligand Metal–Organic Frameworks with Large Pores: Gas Sorption Properties and Single-Crystal-to-Single-Crystal Transformation on Guest Exchange



Two isomorphous 3D metal–organic frameworks, {[Cu2(BPnDC)2(bpy)]8 DMF6 H2O}n (1) and {[Zn2(BPnDC)2(dabco)]13 DMF3 H2O}n (2), have been prepared by the solvothermal reactions of benzophenone 4,4′-dicarboxylic acid (H2BPnDC) with Cu(NO3)22.5 H2O and 4,4′-bipyridine (bpy), and with Zn(NO3)26 H2O and 4-diazabicyclo[2.2.2]octane (dabco), respectively. Compounds 1 and 2 are composed of paddle-wheel {M2(O2CR)4} cluster units, and they generate 2D channels with two different large pores (effective size of larger pore: 18.2 Å for 1, 11.4 Å for 2). The framework structure of desolvated solid, [Cu2(BPnDC)2(bpy)]n (SNU-6; SNU=Seoul National University), is the same as that of 1, as evidenced by powder X-ray diffraction patterns. SNU-6 exhibits high permanent porosity (1.05 cm3 g−1) with high Langmuir surface area (2910 m2 g−1). It shows high H2 gas storage capacity (1.68 wt % at 77 K and 1 atm; 4.87 wt % (excess) and 10.0 wt % (total) at 77 K and 70 bar) with high isosteric heat (7.74 kJ mol−1) of H2 adsorption as well as high CO2 adsorption capability (113.8 wt % at 195 K and 1 atm). Compound 2 undergoes a single-crystal-to-single-crystal transformation on guest exchange with n-hexane to provide {[Zn2(BPnDC)2(dabco)]6 (n-hexane)3 H2O}n (2hexane). The transformation involves dynamic motion of the molecular components in the crystal, mainly a bending motion of the square planes of the paddle-wheel units resulting from rotational rearrangement of phenyl rings and carboxylate planes of BPnDC2−.