Metal-organic frameworks (MOFs) are porous crystalline materials and have attracted tremendous research due to their tunable structures and functions. The features of MOFs have broad potential for gas storage, gas separation, energy conversion, catalysis, sensors, biomedicine, etc. 2D MOFs have layers held by weak interactions, such as hydrogen bonds, van der Waals interactions, and π-π stackings. Three isoreticular hydrogen-bonded 2D MOFs were synthesized from a 1D polymer chain. The 1D polymer chain, Cu(L1)BDC(Cl)2, was constructed from copper(II) and 2,2’-(1H-imidazole-4,5-diyl)di-1,4,5,6-tetrahydropyrimidine, (H-L1). The three isoreticular 2D copper-based MOFs were constructed using different BDC analogues that react with the 1D polymer chain. The pore size and interlayer distance were controlled using different electron-withdrawing groups on the BDC linker. The reaction of Cu(L1)(Cl)2 with the perfluorinated terephthalic acid analogue resulted in Cu(L1)BDC-F4. The fluorinated MOF showed a six-time shorter gas adsorption time with only a slight increase in the channel size between the layers. The pore volume of Cu(L1)BDC-F4 increased three times after modification. The Cu(L1)BDC-Br and Cu(L1)BDC-NO2 analogues increased the interlayer distance of the hydrogen-bonded 2D MOFs. The Cu(L1)BDC family was characterized by PXRD, SCXRD, TGA, FT-IR, etc.

Controlling pore size by electron-withdrawing effects in a 2D layered MOF

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