Xue Zhen-Zhen, Zhang Di, Pan Jie, Han Song-De, Li Jin-Hua, Wang Guo-Ming
College of Chemistry and Chemical Engineering, Qingdao University, Shandong 266071, P. R. China.
Dalton Trans. 2017 Oct 17;46(40):13952-13956. doi: 10.1039/c7dt03339g.
A solvothermal reaction of CuI with a bifunctional organic ligand 3,5-pyridinedicarboxylic acid (Hpdc) afforded a novel heterovalent copper-organic framework, [(CuI)Cu(pdc)(HO)]·4DMSO (1) (DMSO = dimethyl sulfoxide). Compound 1 was structurally characterized by single-crystal X-ray diffraction analyses and further characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD), elemental analyses and thermogravimetric analyses (TGA). Structural analysis indicates that two kinds of common secondary building units (SBUs) coexist in this 3D network. The linkage of Cu and I generates [CuI] subunits and the connection of Cu with carboxyl-O atoms gives rise to binuclear paddle-wheel [Cu(COO)(HO)] moieties. In compound 1, two different SBUs are bridged with pdc ligands to construct a micro-sized cage with an internal spherical cavity. Through a cage-to-cage connection, the 3D porous framework is formed which features intersecting 1D channels. Gas sorption measurements were conducted on the activated 1, showing a H uptake of 1.46 wt% at 77 K and under 1 bar with a high initial adsorption enthalpy of 8.2 kJ mol. Moreover, compound 1 has excellent adsorption selectivity for CO over N and CH.
碘化亚铜与双功能有机配体3,5-吡啶二甲酸（Hpdc）进行溶剂热反应，得到了一种新型的异价铜有机骨架化合物[(CuI)Cu(pdc)(HO)]·4DMSO（1）（DMSO = 二甲基亚砜）。通过单晶X射线衍射分析对化合物1进行了结构表征，并通过红外光谱（IR）、粉末X射线衍射（PXRD）、元素分析和热重分析（TGA）进一步表征。结构分析表明，在这个三维网络中两种常见的二级结构单元（SBUs）共存。Cu和I的连接产生了[CuI]亚单元，而Cu与羧基氧原子的连接形成了双核桨轮状[Cu(COO)(HO)]部分。在化合物1中，两种不同的SBUs通过pdc配体桥连，构建了一个具有内部球形空腔的微米尺寸笼子。通过笼子与笼子之间的连接，形成了具有交叉一维通道的三维多孔骨架。对活化后的1进行了气体吸附测量，结果表明在77 K和1 bar下，其对氢气的吸附量为1.46 wt%，初始吸附焓高达8.2 kJ mol。此外，化合物1对CO相对于N和CH具有优异的吸附选择性。
