Construction of robust open metal-organic frameworks with chiral channels and permanent porosity

摘要

Four new metal-organic frameworks (MOFs) containing chiral channels have been synthesized using an achiral, triazine-based trigonal-planar ligand, 4,4',4' '-s-triazine-2,4,6-triyltribenzoate (TATB), and an hourglass secondary building unit (SBU): Zn-3(TATB)(2)(H2O)(2)center dot 4DMF center dot 6H(2)O (1); Cd-3(TATB)(2)(H2O)(2)center dot 7DMA center dot 10H(2)O (2); [H2N(CH3)(2)][Zn-3(TATB)(2)(HCOO)]center dot HN(CH3)(2)center dot 3DMF center dot 3H(2)O (3); [H2N(CH3)(2)][Cd-3(TATB)(2)(CH3COO)]center dot HN(CH3)(2)center dot 3DMA center dot 4H(2)O (4). MOFs 1 and 2 are isostructural and possess (10,3)-a nets containing large chiral channels of 20.93 and 21.23 angstrom, respectively, but are thermally unstable due to the easy removal of coordinated water molecules on the SBU. Replacement of these water molecules by formate or acetate generated in situ leads to 3 and 4, respectively. Formate or acetate links SBUs to form infinite helical chains bridged by TATB to create three-dimensional anionic networks, in which one of the two oxygen atoms of the formate or acetate is uncoordinated and points into the void of the channels. This novel SBU-stabilization and channel-functionalization strategy may have general implications in the preparation of new MOFs. Thermogravimetric analysis (TGA) shows that solvent-free 3' is thermally stable to 410 degrees C, while TGA studies on samples vapor-diffused with water, methanol, and chloroform show reversible adsorption. MOF 3 also has permanent porosity with a large Langmuir surface area of 1558 m(2)/g. All complexes exhibit similar strong luminescence with a lambda(max) of approximately 423 nm upon excitation at 268.5 nm.