二茂铁功能化的两例镉金属有机框架材料的合成、结构和表征※

doi:10.6023/A21120611

摘要/Abstract

含有二茂铁单元的1,1'-二茂铁二羧酸(H₂FcDCA)是构筑具有氧化还原活性的金属有机框架(MOFs)的理想配体, 然而由于其不可控的配位模式和扭转角, 目前基于H₂FcDCA的配合物的合成仍然具有挑战性. 本工作中, 利用H₂FcDCA与Cd²⁺反应合成了2个新颖的MOFs. 化合物1中, 镉中心被FcDCA和4,4'-联吡啶(bpy)桥连形成二维层. 在该体系中引入草酸则实现了三维框架的构筑(化合物2). 和1不同, 2中具有双核Cd₂单元, 该单元通过bpy和草酸连接形成具有金刚石型拓扑的框架, FcDCA同时作为功能单元和孔分割配体. 这2个化合物都表现出可见光吸收、光电流响应和典型的二茂铁氧化还原特性, 这些特性使其在光电催化方面具有潜在的应用前景.

关键词: 金属有机框架, 单晶结构, 光电流, 循环伏安, 二茂铁

Metal-organic frameworks (MOFs) are one of the most important crystalline porous materials. In recent years, there has been a strong interest in MOFs based devices with electrochemical activity. MOFs with redox activity are the ideal choice for such devices. 1,1'-Ferrocene dicarboxylic acid (H₂FcDCA) containing ferrocene units is an ideal ligand for constructing MOFs with redox activity. However, due to its uncontrollable coordination mode and torsion angle, there is still a challenge to construct such materials. In this paper, two MOFs were synthesized by the reaction of functional ligand H₂FcDCA with Cd²⁺ under different hydrothermal conditions: [Cd(FcDCA)(bpy)(H₂O)]•(bpy) (1) (bpy=4,4'-bipyridine) and [Cd₂(FcDCA)(bpy)(OX)(H₂O)₂]•2H₂O (2) (H₂OX=oxalic acid). The single crystal structure, fluorescence properties, redox activity of two compounds were characterized and described. In compound 1, Cd center was linked by FcDCA to form a zigzag chain, and it was linked by bpy to form a chain. Both chains linked each other by sharing the Cd center to give birth to a 2D layer with square lattice topology (sql). These layers were packed in AA mode along ac plane. Bpy as guest molecules are filled in the channel of it. By introducing H₂OX in this system under similar condition, compound 2 with 3D framework was obtained. Different to compound 1, two Cd atoms were coordinated by OX ligands to form a binuclear Cd₂ unit. The Cd₂ units were connected by bpy and OX ligands to form a 3D framework with typical 4-connected diamond topology (dia). Each FcDCA ligand linked two Cd₂ units as functional unit and pore partition agent. The whole framework of compound 2 can be simplified as 6-connected sxd topology by treating three kinds of ligands FcDCA, bpy and OX as linkers. Both compounds exhibited strong visible light absorption ability, photocurrent response, and typical redox properties of ferrocene, which may be good candidates for photoelectric catalysts.

Key words: metal-organic frameworks (MOFs), single crystal structure, photocurrent, cyclic voltammetry, ferrocene

引用此文

张容, 柳江萍, 朱子怡, 陈淑妹, 王飞, 张健. 二茂铁功能化的两例镉金属有机框架材料的合成、结构和表征^※[J]. 化学学报, 2022, 80(3): 249-254.

Rong Zhang, Jiangping Liu, Ziyi Zhu, Shumei Chen, Fei Wang, Jian Zhang. Synthesis, Structure and Characterization of Two Ferrocene Functionalized Cadmium Metal Organic Frameworks^※[J]. Acta Chimica Sinica, 2022, 80(3): 249-254.

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图/表 6

图1. 化合物1的结构图: (a) 1的配位环境图; (b) FcDCA-Cd和bpy-Cd的1D链; (c) 沿着ac面形成2D层状结构; (d) b轴上的堆积. 为了更清楚显示结构. 部分氢原子已被删除

Figure 1. Structures of compound 1: (a) Coordination environment of 1; (b) Illustrations of 1D FcDCA-Cd and 1D bpy-Cd; (c) 2D layered structure along the ac plane; (d) b axis pack. Some hydrogen atoms are removed for clarity

图2. 化合物2的结构图: (a) 2中的双核镉单元及其简化的6-连接节点, 氢键相关的部分氢原子保留; (b) 草酸、联吡啶和二茂铁羧酸作为桥连配体分别简化为三种不同的连接体; (c) 沿a轴方向显示的三维框架; (d) 简化的6-连接sxd拓扑; (e) 草酸和联吡啶连接双核镉单元形成的三维框架; (f) 及其对应的金刚石拓扑

Figure 2. Structures of compound 2: (a) the Cd2 SBUs and simplified 6-connected node of 2; parts of hydrogen atoms are kept for clear exhibition of the H-bonds; (b) bpy, OX and FcDCA as linkers; (c) view of the 3D framework along a axis; (d) the simplified 6-connected sxd topology; (e) view of the 3D framework only constructed by bpy and OX ligands; (f) 4-connected dia topology

图3. (a) 化合物1的UV-Vis DRS; (b) 化合物2的UV-Vis DRS

Figure 3. (a) UV-Vis DRS of 1; (b) UV-Vis DRS of 2

图4. 化合物1和2的光电流测试

Figure 4. Photocurrent test of compounds 1 and 2

图5. 化合物1和2 (第20周期)的循环伏安图

Figure 5. Cyclic voltammograms for the compounds 1 and 2 (20th cycle)

图6. 1,1'-二茂铁二羧酸(H2FcDCA)配体和化合物1和2的荧光发射图

Figure 6. Normalized emission spectra measured for the H2FcDCA ligand and compounds 1 and 2

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