Steric Effect Modulating the Structures of Trinuclear Zinc Carboxylate Frameworks

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By the reaction of different aromatic dicarboxylic acid with zinc nitrate, three metal-carboxylate frameworks, [Zn_3(BDC)_3(EtOH)_2](1), [Zn_3(BDC)_3(py)_2]·2DMF(2), and [Zn_3(NH_2-BDC)_3(H_2O)_2]·5DMF(3) which are constructed on the same linear trinuclear Zn_3(RCOO)_6 secondary building units, have been synthesized and characterized by X-ray diffraction analyses. Structural analyses showed that there are terephthalic acids as ligand linkers to form the hxl topological layer structures for 1 and 2. The introduction of the rigid aromatic ring pyridine in 2 as the terminal co-ligand of Zn3-SBU to instead of the flexible ethanol in 1, will form the layer-pillared supramolecular systems with 2-D crisscross channels, through its π-π stacking interactions. Owing to the steric hindrance of amino groups, 3 was assembled into a three-dimensional porous structure with pcu topology derived from the 2-amino-terephthalic acid as linkers to connect the Zn3-SBUs through a head-to-tail type. By the reaction of different aromatic dicarboxylic acid with zinc nitrate, three metal-carboxylate frameworks, [Zn_3 (BDC) _3 (EtOH) _2] (1), [Zn_3 (BDC) _3 and [Zn_3 (NH_2-BDC) _3 (H_2O) _2] · 5DMF (3) which are constructed on the same linear trinuclear Zn_3 (RCOO) _6 secondary building units, have been synthesized and characterized by X-ray analysis. showed that there are terephthalic acids as ligand linkers to form the hxl topological layer structures for 1 and 2. The introduction of the rigid aromatic ring pyridine in 2 as the terminal co-ligand of Zn3-SBU to instead of the flexible ethanol in 1, will form the layer-pillared supramolecular systems with 2-D crisscross channels, through its π-π stacking interactions. Owing to the steric hindrance of amino groups, 3 was assembled into a three-dimensional porous structure with pcu topology derived from the 2- amino-terephthalic acid as linkers to connect the Zn3-SBUs through a head-to-tail type.
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