化学学报 ›› 2022, Vol. 80 ›› Issue (3): 249-254.DOI: 10.6023/A21120611 上一篇    下一篇

研究通讯

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

张容a,b, 柳江萍a,b, 朱子怡a,b, 陈淑妹a,*(), 王飞b,*(), 张健b   

  1. a 福州大学 化学学院 福州 350108
    b 中国科学院福建物质结构研究所 结构化学国家重点实验室 福州 350002
  • 投稿日期:2021-12-31 发布日期:2022-02-17
  • 通讯作者: 陈淑妹, 王飞
  • 作者简介:
    庆祝中国科学院青年创新促进会十年华诞.
  • 基金资助:
    国家自然科学基金(21871050)

Synthesis, Structure and Characterization of Two Ferrocene Functionalized Cadmium Metal Organic Frameworks

Rong Zhanga,b, Jiangping Liua,b, Ziyi Zhua,b, Shumei Chena(), Fei Wangb(), Jian Zhangb   

  1. a College of Chemistry, Fuzhou University, Fuzhou 350108, China
    b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
  • Received:2021-12-31 Published:2022-02-17
  • Contact: Shumei Chen, Fei Wang
  • About author:
    Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
  • Supported by:
    National Natural Science Foundation of China(21871050)

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