Wang Yan-Ning, Yang Qing-Feng, Li Guang-Hua, Zhang Ping, Yu Jie-Hui, Xu Ji-Qing
College of Chemistry, Jilin University, Jiefang Road 2519, Changchun, 130023, P.R. China.
Dalton Trans. 2014 Aug 14;43(30):11646-57. doi: 10.1039/c4dt00780h. Epub 2014 Jun 19.
Under hydrothermal conditions, the reactions of Ba(2+)/Zn(2+), aromatic polycarboxylic acids and N2H4 with or without oxalic acid were carried out, affording four new acylhydrazidate-extended metal-organic frameworks (MOFs) [Ba(pmdh)] (pmdh = pyromellitdihydrazidate) 1, [Ba(sdpth)(H2O)2]·0.5H2O (sdpth = 4,4'-sulfoyldiphthalhydrazidate) 2, [Ba2(cpth)2(H2O)2] (cpth = 4-carboxylphthalhydrazidate) 3 and [Zn2(pdh)2(ox)]·H2O (ox = oxalate, pdh = pyridine-2,3-dicarboxylhydrazidate) 4. The acylhydrazidate molecules pmdh, sdpth, cpth and pdh in compounds 1-4 derived from the hydrothermal in situ acylation of N2H4 with aromatic polycarboxylic acids. X-ray single-crystal diffraction analysis revealed that (i) in compound 1, the pmdh I molecules link the Ba(2+) ions into a two-dimensional (2D) layer with a (4,4) topology, and then the pmdh II molecules extend these layers into a three-dimensional (3D) network; (ii) in compound 2, the sdpth molecules link the Ba(2+) ions to form a one-dimensional (1D) square tube. Interestingly, the tubes are further linked into a 3D supramolecular network via the N-H···O interactions, creating synchronously big channels; (iii) in compound 3, the cpth I molecules link the Ba1 ions into a 3D network with a (10,3) topology. Ba2 and cpth II are distributed on the channels; (iv) in compound 4, Zn(2+) and pdh aggregate to form two types of Zn4(pdh)4 clusters. The ox molecules act as the secondary linkers, extending the Zn4(pdh)4 secondary building units (SBUs) into a 3D network with a 6(6) topology. The photoluminescence analysis indicates that compounds 3 and 4 emit green light with maxima at 495 nm for 3 (λ(ex) = 397 nm), and 522 nm for 4 (λ(ex) = 395 nm), respectively. At 77 K, the activated 2 and 4 can adsorb N2 in amounts of 58.31 cm(3) g(-1) for 2 and 38.38 cm(3) g(-1) for 4, respectively.
在水热条件下，进行了Ba(2+)/Zn(2+)、芳香多元羧酸与N2H4在有或没有草酸存在时的反应，得到了四种新型酰肼基延伸的金属有机框架（MOF）：[Ba(pmdh)]（pmdh = 均苯四甲酸二酰肼）1、[Ba(sdpth)(H2O)2]·0.5H2O（sdpth = 4,4'-磺酰二邻苯二甲酰肼）2、[Ba2(cpth)2(H2O)2]（cpth = 4-羧基邻苯二甲酰肼）3和[Zn2(pdh)2(ox)]·H2O（ox = 草酸根，pdh = 吡啶-2,3-二羧酸酰肼）4。化合物1-4中的酰肼基分子pmdh、sdpth、cpth和pdh源自N2H4与芳香多元羧酸的水热原位酰化反应。X射线单晶衍射分析表明：（i）在化合物1中，pmdh I分子将Ba(2+)离子连接成具有(4,4)拓扑结构的二维（2D）层，然后pmdh II分子将这些层扩展成三维（3D）网络；（ii）在化合物2中，sdpth分子连接Ba(2+)离子形成一维（1D）方管。有趣的是，这些管通过N-H···O相互作用进一步连接成3D超分子网络，同时形成大通道；（iii）在化合物3中，cpth I分子将Ba1离子连接成具有(10,3)拓扑结构的3D网络。Ba2和cpth II分布在通道上；（iv）在化合物4中，Zn(2+)和pdh聚集形成两种类型的Zn4(pdh)4簇。草酸根分子作为二级连接体，将Zn4(pdh)4二级构筑单元（SBU）扩展成具有6(6)拓扑结构的3D网络。光致发光分析表明，化合物3和4分别发射绿光，最大发射波长对于3为495 nm（激发波长λ(ex)=397 nm），对于4为522 nm（激发波长λ(ex)=395 nm）。在77 K时，活化后的2和4分别能够吸附N2，吸附量对于2为58.31 cm(3) g(-1)，对于4为38.38 cm(3) g(-1)。
