Structural diversification and single-crystal-to-single-crystal transformation of alkaline earth metal-based MOFs regulated by solvent effect

摘要

Two pairs of alkaline earth metal-based MOFs have been synthesized by spontaneous self-assembly reactions of Mg(II) or Ca(II) and two tricarboxylate ligands, H3BTTB and H3TCM (H3BTTB = 4,4',4 ''-[benzene-1,3,5-triyl-tris(oxy)]tribenzoic acid; H3TCM = 4,4',4 ''-{[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(oxy)} tribenzoic acid), in different solvent media. The Mg/BTTB assemblies, {[Mg-3/2(BTTB)(H2O)(DMF)](DMF)}(n) (1) (DMF = N, N'-dimethylformamide) and {[Mg-3/2(BTTB)(DMAc)(2)](DMAc)(0.5)}(n) (2) (DMAc = N, N'-dimethylacetamide), are prepared in DMF/H2O and DMAc/H2O media, respectively, and feature uniform kgd-type 2D bilayer structures but with different compactness. Meanwhile, two Ca/TCM assemblies, {[Ca-5/2(TCM)(2)(DMF)(2)(H2O)](Me2NH2)(DMF)(2)(H2O)}(n) (3) and {[Ca-3(TCM)(2)(DMAc)(3)(H2O)(2)](DMAc)(5)}(n) (4), have been achieved in DMF/H2O and DMAc/H2O mixed systems as well. However, compounds 3 and 4 have an enormous structural discrepancy, that is, compound 3 shows a complicated parallel 2D -> 3D polycatenaned supramolecular architecture while 4 exhibits a 2-fold interpenetrating sit-type 3D framework. These various coordination patterns evidently illustrate the solvent regulation on the alkaline earth metal-based MOFs. The single-crystal-to-single-crystal structural transformation experiment reveals that the loose kgd-network compound 2 can be converted into the compact isoreticular compound 1 when immersed in DMF for 12 h. However, the reversed conversion cannot be realized. In addition, their thermal stability, gas adsorption, and solid-state fluorescence properties have also been investigated.