Azo Functionalized 5-Nitro-1,3-benzenedicarboxylate Based Coordination Polymers with Different Dimensionality and Functionality

作者：Maity Dilip Kumar; Halder Arijit; Ghosh Saheli; Ghoshal Debajyoti^*

来源：Crystal Growth & Design, 2016, 16(9): 4793-4804.

DOI：10.1021/acs.cgd.6b00946

Five azo-functionalized coordination polymers (CPs), namely, [Zn(azbpy)(NO2-bdc)center dot H2O](n) (1), [Zn(azbpy)(NO2-bdc)]n center dot 3H(2)O (2), {[Cd(azbpy)(NO2-bdc)center dot H2O]center dot 2H(2)O}, (3), {[Mn(azbpy)(2)(NO2-bdc)](2)}n (4), and {[Co(azbpy)(NO2- bdc)(H2O)(2)] [Co (azbpy)(0.5) (NO2-bdC) (H2O)(3)]}(n) (5) have been synthesized using different transition metal salts with 5-nitro-1,3benzenedicarboxylate (NO2-bdc(2-)) and 4,4'-azobispyridine (azbpy) ligand using a slow diffusion technique at room temperature. The complexes 1-5 were characterized by single crystal X-ray diffraction analysis, elemental analysis, infrared spectroscopy (IR), powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). In the solid state, compound 1 shows a wavy one-dimensional (1D) ladder; constructed through the N/N'-donor azbpy and NO2-bdc(2-) ligands with the metal centers, whereas compound 2 exhibits a bilayer two-dimensional (2D) sheet containing a wavy 1D ladder of metal-carboxylate, and compound 3 shows a stairlike wavy 2D sheet. Compound 4 exhibits a novel 2-fold interdigitated 2D sheet of two similar layers containing pendent azbpy ligands, whereas compound 5 displays a polythreaded 2D structure with an intercalated 1D chain into the pore. The solid state luminescence properties of 1-3 along with free N,N'-donor azbpy ligand have been performed at room temperature, where all the complexes 1-3 show azbpy ligand based luminescence property. The gas and solvent vapor adsorption study have been performed for compounds 2-4, and the dehydrated frameworks of compounds 2-4 exhibit selective CO2 adsorption at 195 K over N-2 (at both 77 and 195 K) due to the strong interactions between polar pore walls of dehydrated frameworks with the CO2 molecule having quadruple moment.

• 出版日期2016-9