MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, PR China.
Dalton Trans. 2011 Sep 14;40(34):8549-54. doi: 10.1039/c1dt10682a. Epub 2011 Jul 26.
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).
在不同条件下，通过锌（NO3）2、1,4-苯二甲酸（H2bdc）和 4,4'-联吡啶（azpy）的溶剂热反应得到了[Zn（bdc）（bphy）]·DMF·H2O（1a，bphy=1,2-双（4-吡啶基）肼，DMF=N,N-二甲基甲酰胺）和[Zn（bdc）（bphy）]·EtOH·H2O（1b），具有两倍穿插的 dmp 拓扑结构，以及[Zn2（bdc）2（bphy）]·1.5EtOH·H2O（2a）和[Zn2（bdc）2（bphy）]·DMA·1.5H2O（2b，DMA=N,N-二甲基乙酰胺），具有两倍穿插的 pcu 拓扑结构。通过单晶结构、酸消解晶体样品的 LC-MS 分析以及控制溶剂热实验证实了 azpy 原位还原为 bphy。1a/1b 和 2a/2b 中客体分子的去除将材料转化为无客体相[Zn（bdc）（bphy）]（1）和[Zn2（bdc）2（bphy）]（2），这通过 PXRD 得到了证实。在 195 和 298 K 下进行的 CO2 吸附实验表明，1 的孔隙率较低，2 的吸附行为具有门控性。在 298 K 下，2 对吸附 CO2 具有高选择性，对 CH4 的吸附选择性较低。
