Flexible porous coordination polymers constructed from 1,2-bis(4-pyridyl)hydrazine via solvothermal in situ reduction of 4,4'-azopyridine |
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Authors: | Liu Xiao-Min Xie Lin-Hua Lin Jian-Bin Lin Rui-Biao Zhang Jie-Peng Chen Xiao-Ming |
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Institution: | MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, PR China. |
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Abstract: | Solvothermal reactions of Zn(NO(3))(2), 1,4-benzenedicarboxylic acid (H(2)bdc), and 4,4'-azopyridine (azpy) in different conditions yielded Zn(bdc)(bphy)]·DMF·H(2)O (1a, bphy = 1,2-bis(4-pyridyl)hydrazine, DMF = N,N-dimethylformamide) and Zn(bdc)(bphy)]·EtOH·H(2)O (1b) with two-fold interpenetrated dmp topology and Zn(2)(bdc)(2)(bphy)]·1.5EtOH·H(2)O (2a) and Zn(2)(bdc)(2)(bphy)]·DMA·1.5H(2)O (2b, DMA = N,N-dimethylacetamide) with two-fold interpenetrated pcu topology. The in situ reduction of azpy to bphy was confirmed by single-crystal structures and LC-MS analyses of the acid-digested crystalline samples, as well as controlled solvothermal experiments. Removal of the guest molecules in 1a/1b and 2a/2b converts the materials to guest-free phases Zn(bdc)(bphy)] (1) and Zn(2)(bdc)(2)(bphy)] (2), respectively, which were identified by PXRD. CO(2) sorption experiments performed at 195 and 298 K showed low porosity for 1 and gated sorption behavior for 2. At 298 K, 2 exhibits high selectivity for adsorbing CO(2) over CH(4). |
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