Urea-based flexible dicarboxylate linkers for three-dimensional metal-organic frameworks
Urea-based flexible dicarboxylate linkers for three-dimensional metal-organic frameworks
复制标题
DOI：
10.1016/j.ica.2017.09.029
复制
发表时间：
2017-09
影响因子：
2.8
通讯作者：
Sebastian Glomb;Gamall Makhloufi;Irina Gruber;C. Janiak
中科院分区：
文献类型：
--
作者：
Sebastian Glomb;Gamall Makhloufi;Irina Gruber;C. Janiak
金属有机骨架(MOF) 3D-[Mn2(L1)2(DMF)]·2DMF (1)、3D-[Cd2(L2)2(DMF)3] (3)、[Zn2(L2)2(DMF)3] (4) 和 3D-[Mn2(L2)2(DMF)3] (5) 是三维材料的第一个例子。 由单个二位二羧酸酯连接体（即，没有桥联共配体）构建的金属有机网络，连接体轴上有一个脲基团（L12−= 4,4′-（羰基双（氮杂二基））二苯甲酸酯； L22−= 4,4′-(羰基双(氮杂二基))双(3-甲基苯甲酸酯)，DMF = 二甲基甲酰胺)。由 Cd2+ 和 L12- 形成一维配位聚合物 1D-[Cd(L1)(DMF)3] (2)。脲基团与 C(4)[R12(6)] 基序通过氢键与 DMF 溶剂 (in1) 或金属配位的羧酸盐基团 (in3-5) 的氧原子形成氢键。 Network1 具有无限通道，具有平行六面体横截面和 30% 的溶剂填充体积。 3D 框架 3-5 是金刚石 (6,6)，具有单一框架的硅拓扑结构，具有 17.6 Å 和 19.7 Å 节点间距的大空隙。因此，四个对称相关网络相互渗透，通过 C(4)[R12(6)] 基序中的氢键组织，在四重互穿结构中仍然留下约 50% 的溶剂填充空隙体积。
The metal-organic frameworks (MOFs) 3D-[Mn2(L1)2(DMF)]·2DMF (1), 3D-[Cd2(L2)2(DMF)3] (3), [Zn2(L2)2(DMF)3] (4) and 3D-[Mn2(L2)2(DMF)3] (5) are the first examples of three-dimensional metal-organic networks constructed from a single ditopic dicarboxylate linker (i.e., without bridging co-ligands) with an urea group in the linker axis (L12−= 4,4′-(carbonylbis(azanediyl))dibenzoate; L22−= 4,4′-(carbonylbis(azanediyl))bis(3-methylbenzoate), DMF = dimethylformamide). From Cd2+and L12−a 1D coordination polymer 1D-[Cd(L1)(DMF)3] (2) is formed. The urea group is engaged in hydrogen bonding with the C(4)[R12(6)] motif to an oxygen atom of a DMF solvent (in1) or a metal-coordinated carboxylate group (in3–5). Network1has infinite channels with parallelepiped cross sections and 30% solvent-filled volume. The 3 D frameworks3–5are of diamond (6,6),diatopology with a single framework having large voids with 17.6 Å and 19.7 Å nodal separation. Thus, four symmetry-related nets interpenetrate, organized via H-bonds in the C(4)[R12(6)] motif, still leaving about 50% solvent-filled void volume in the fourfold interpenetrated structure.