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

doi:10.6023/A21120611

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (3): 249-254.DOI: 10.6023/A21120611 Previous Articles Next Articles

Special Issue: 中国科学院青年创新促进会合辑

Communication

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

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 Zhang^a^,^b, Jiangping Liu^a^,^b, Ziyi Zhu^a^,^b, Shumei Chen^a(), Fei Wang^b(), Jian Zhang^b

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)

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Abstract

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

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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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Fig. & Tab. 6

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

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

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

Figure 4. Photocurrent test of compounds 1 and 2

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

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

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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^※

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

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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※

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

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PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 6

References 31

Related Articles 15

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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^※

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