Synthesis, Structure, and Properties of [Cu2(HBTC)2(4, 4′-bpy)2·5H2O] Complex

doi:10.16553/j.cnki.issn1000-985x.2025.0098

Abstract

Abstract: A two-dimensional （2D） copper-based metal-organic framework （MOF），［Cu₂（HBTC）₂（4， 4′-bpy）₂·5H₂O］（complex 1）， was successfully synthesized via a hydrothermal method， using 1， 3， 5-benzenetricarboxylic acid （H₃BTC） and 4， 4′-bipyridine （4， 4′-bpy） as organic ligands， and Cu（Ac）₂·H₂O as the copper source. The structure of complex 1 was determined by X-ray diffraction， elemental analysis， and Fourier-transform infrared spectroscopy （FT-IR）. The results show that complex 1 belongs to the monoclinic crystal system， space group C2/c， with the asymmetric unit containing one Cu²⁺， one deprotonated HBTC^2-， one 4， 4′-bpy， and three crystalline water molecules. In the exploration of organic dye adsorption capabilities， complex 1 demonstrates an excellent selective adsorption performance for methylene blue， achieving a removal rate of up to 93.4%. In addition， complex 1 shows a proton conductivity of 7.32×10^-4 S·cm^-1 at 65 ℃ and 98% RH. This study provides new insights into the application of MOFs in dye adsorption and proton conductive materials.

Key words: copper-based complex; crystal structure; metal-organic framework; dye adsorption; proton conduction

CLC Number:

O641

ZHANG Shan, LIU Ling, FENG Jianxuan, CHEN Qiangqiang, WU Hongmei, GUO Yu. Synthesis, Structure, and Properties of [Cu₂(HBTC)₂(4, 4′-bpy)₂·5H₂O] Complex[J]. Journal of Synthetic Crystals, 2025, 54(11): 1961-1966.

Figures/Tables 7

Table 1 Crystallographic data of complex 1

Complex	1
Formula	Cu₂C₃₈N₄O₁₇H₃₄
Formula weight	945.77
Temperature/K	284.58
Crystal system	Monoclinic
Space group	C2/c
a/Å	12.191 0（9）
b/Å	20.927 0（15）
c/Å	15.232 5（11）
α/（°）	90
β/（°）	107.269（3）
γ/（°）	90
Volume/Å³	3 710.9（5）
Z	4
D_calc/（g·cm^-3）	1.693
μ/mm^-1	1.234
F（000）	1 936.0
Reflections collected	22 895
Independent reflections	3 307 ［R_int=0.085 0］
GOOF	1.074
Final R indexes ［I>=2σ（I）］	R₁=0.036 5， wR₂=0.078 6
Final R indexes ［all data］	R₁=0.069 7， wR₂=0.094 5

Fig.1 Coordination environment （a）， 2D grid structure （b）， and topological structure （c） of complex 1 （#1： -1/2+X， 1/2-Y， 1/2+Z； #2： 1/2-X， 1/2+Y， 1/2-Z）

Fig.2 Layered stacking structure （a） and 3D supramolecular structure （b） of complex 1

Table 2 Hydrogen bonding interactions in complex 1

D—H…A	d （D—H）/Å	d （H…A）/Å	d （D…A）/Å	∠（D—H…A）/（^o）
O4—H4…O1（W）	0.82	1.806	2.616	169.64
O2（W）—H2WA…O2	0.85	1.882	2.710	164.39
O3（W）—H3WA…O6	0.84	2.154	2.817	134.80
O2（W）—H2WB…O3	0.85	2.432	2.994	124.29

Fig.3 Photograph （a）， microscopic morphology （b）， and PXRD patterns （c） of complex 1

Fig.4 Dye adsorption performance of complex 1. （a） Change of MB removal rate over time；（b） adsorption effect on a mixed solution of MB and MO

Fig.5 Proton conduction performance. （a） Nyquist plots of complex 1 under 25~75 ℃ and 98% RH；（b） hydrogen bond network and continuous water molecule chains exist in the structure of complex 1

References 20

[1]	SUN N N， SHAH S S A， LIN Z Y， et al. MOF-based electrocatalysts： an overview from the perspective of structural design［J］. Chemical Reviews， 2025， 125（5）： 2703-2792.
[2]	HAYAT A， RAUF S， ALWAN BAL， et al. Recent advance in MOFs and MOF-based composites： synthesis， properties， and applications［J］. Materials Today Energy， 2024， 41： 101542.
[3]	WU M M， SUN Y W， JI T T， et al. Fabrication of water-stable MOF-808 membrane for efficient salt/dye separation［J］. Journal of Membrane Science， 2023， 686： 122023.
[4]	ZHAO T J， WU H Y， WEN X H， et al. Recent advances in MOFs/MOF derived nanomaterials toward high-efficiency aqueous zinc ion batteries［J］. Coordination Chemistry Reviews， 2022， 468： 214642.
[5]	HASSAN H， UMAR E， IQBAL M W， et al. Innovative MOF-5/V₂CT _x composite for high-performance， and ultra-fast supercapacitors and hydrogen evolution reaction［J］. Electrochimica Acta， 2024， 489： 144277.
[6]	LIU Y R， CHEN Y Y， ZHAO H Y， et al. Exploration of single-crystal proton conduction in ordered networks［J］. Coordination Chemistry Reviews， 2024， 499： 215516.
[7]	孙丽君，吕雪燕，丁陆阳，等. 金属有机框架/离子液体增强的质子交换膜的制备及性能［J］. 材料工程， 2024， 52（8）： 150-158.
	SUN L J， LYU X Y， DING L Y， et al. Preparation and properties of proton exchange membrane reinforced by metal-organic framework/ionic liquid［J］. Journal of Materials Engineering， 2024， 52（8）： 150-158 （in Chinese）.
[8]	ZHU L Y， YANG H B， XU T， et al. Precision-engineered construction of proton-conducting metal-organic frameworks［J］. Nano-Micro Letters， 2024， 17（1）： 87.
[9]	WU W L， FENG L， TAN W， et al. Influence of activated protons and acid-base pairs on proton conduction in imino-functionalized MOF-based hybrid membranes［J］. Process Safety and Environmental Protection， 2024， 186： 1263-1272.
[10]	NAJAFI M， ABEDNATANZI S， GOHARI DERAKHSHANDEH P， et al. Metal-organic and covalent organic frameworks for the remediation of aqueous dye solutions： adsorptive， catalytic and extractive processes［J］. Coordination Chemistry Reviews， 2022， 454： 214332.
[11]	XIANG W Q， WANG Q， LI Z J， et al. Water-stable methyl-modified MOF and mixed matrix membrane for efficient adsorption and separation of cationic dyes［J］. Separation and Purification Technology， 2024， 330： 125268.
[12]	GAYATHRI K， VINOTHKUMAR K， MOHAN S， et al. Manifestation of UiO-66-Zr MOF-enabled photocatalytic membranes for successive separation and degradation of dye mixtures in water remediation［J］. Journal of Environmental Chemical Engineering， 2024， 12（3）： 112490.
[13]	ELSHERBINY A S， RADY A， ABDELHAMEED R M， et al. Efficiency and selectivity of cost-effective Zn-MOF for dye removal， kinetic and thermodynamic approach［J］. Environmental Science and Pollution Research International， 2023， 30（49）： 106860-106875.
[14]	LIU X D， WANG X C， XU N， et al. A multifunctional｛P₂Mo₅｝-based hybrid applying to catalysis， electrocatalysis and dye adsorption［J］. Chemical Research in Chinese Universities， 2022， 38（6）： 1553-1560.
[15]	SHI Y W， CHANG Q， ZHANG T W， et al. A review on selective dye adsorption by different mechanisms［J］. Journal of Environmental Chemical Engineering， 2022， 10（6）： 108639.
[16]	GUO S J， ZOU Z Y， CHEN Y， et al. Synergistic effect of hydrogen bonding and π-π interaction for enhanced adsorption of rhodamine B from water using corn straw biochar［J］. Environmental Pollution， 2023， 320： 121060.
[17]	SALAHSHOORI I， NAMAYANDEH JORABCHI M， GHASEMI S， et al. Advancements in wastewater treatment： a computational analysis of adsorption characteristics of cationic dyes pollutants on amide functionalized-MOF nanostructure MIL-53 （Al） surfaces［J］. Separation and Purification Technology， 2023， 319： 124081.
[18]	ZHANG S， LU Y， SUN X W， et al. Proton transfer in polyamine-P₂Mo₅ model adducts： exploring the effect of polyamine cations on their proton conductivity［J］. Dalton Transactions， 2020， 49（47）： 17301-17309.
[19]	WANG M M， CAI J J， LUN H J， et al. Design and analysis of POM-guanidine compounds： achieving ultra-high single-crystal proton conduction［J］. Advanced Functional Materials， 2024， 34（7）： 2311912.
[20]	OGIWARA N， IWANO T， ITO T， et al. Proton conduction in ionic crystals based on polyoxometalates［J］. Coordination Chemistry Reviews， 2022， 462： 214524.

Synthesis, Structure, and Properties of [Cu₂(HBTC)₂(4, 4′-bpy)₂·5H₂O] Complex

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 7

References 20

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	CHEN Wentao, ZHUANG Xingyi, AN Hangyi, LAI Zhongjie, WANG Airong, LUO Yani, SHI Zhongfeng, LI Jiaming. Synthesis, Crystal Structure, and Fluorescence Sensing Property in Water by a Two-Dimensional Cobalt Metal-Organic Framework [J]. Journal of Synthetic Crystals, 2025, 54(9): 1642-1653.
[2]	JIN Yuxi, YU Haili, WANG Yuqing, XIE Longchen, TIAN Hongrui, CHEN Baokuan. Synthesis， Crystal Structure and Magnetic of Di-Nuclear V^IV Complex [J]. Journal of Synthetic Crystals, 2025, 54(6): 1021-1026.
[3]	XU Tongtao, WAN Hongshan, YANG Tianxing, GAO Min, WANG Chong. Synthesis, Characterization and Properties of Two Coppper(Ⅱ) Complexes Derived from 4-Amino-2,6-Dimethoxypyrimidine [J]. Journal of Synthetic Crystals, 2025, 54(4): 684-692.
[4]	LI Jia, FENG Jing, MIAO Meng. Crystal Structure and Magnetism of Two Isomorphic Complexes Based on Mixed Ligands [J]. Journal of Synthetic Crystals, 2025, 54(4): 693-699.
[5]	LI Kehua, YI Kuiyu, SHI Hongwei, KANG Xiaoqi. Research Progress on Fluorescence Detection of Antibiotics by Metal-Organic Frameworks [J]. Journal of Synthetic Crystals, 2025, 54(11): 1881-1892.
[6]	SUN Wentao, XU Yan, FENG Lushun, MENG Wenqing, ZHENG Weijian, LI Xinxing, LI Suzhi. Synthesis, Crystal Structure and Magnetic Properties of Metal Organic Cobalt Phosphonates Complexes Based on Chiral/Racemic Ligands [J]. Journal of Synthetic Crystals, 2025, 54(11): 1974-1982.
[7]	ZHANG Shan, FENG Jianxuan, LIU Ling, GUO Yu. Green and Efficient Oxidation of Sulfides to Sulfoxides Catalyzed by Vanadium-Based Complex [J]. Journal of Synthetic Crystals, 2025, 54(11): 1983-1989.
[8]	LU Xinyi, WANG Ruixi, LI Mengyue, WU Liming, CHEN Ling. NaCeF(SO₄)₂: Synthesis Structure of New Cerium Fluoride Sulfate and Its Nonlinear Optical Property [J]. Journal of Synthetic Crystals, 2025, 54(10): 1772-1779.
[9]	LI Miao, ZHENG Yimeng, SUN Yiting, MAO Yuling, ZHU Baili, CUI Shuxin. Preparation and Properties of a Cadmium Coordination Compound with 4,5-Imidazoledicarboxylic Acid [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2025, 54(1): 121-125.
[10]	XU Yarong, ZHAO Jiuzhou, ZHAO Chengxiong, LIANG Yinong, SUN Zan. Synthesis, Structure and Hirshfeld Analysis of Zn Coordination Polymer Based on 1,3-Benzodioxole-5-Carboxylic Acid and 4,4′-Bipyridine [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2025, 54(1): 115-120.
[11]	WANG Xinying, QIAO Decong, PAN Huibin, GAO Xia, LU Jiufu. Cd(Ⅱ)-Based Fluorescent Sensing Organic Framework Constructed by Mixed Ligands and Its Performance [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2025, 54(1): 126-132.
[12]	JIAO Sihui, WU Hongping, YU Hongwei. CsBa₂ScB₈O₁₆: the First Rare-Earth Borate Simultaneously Containing Zero-Dimensional [B₃O₆] Units and One-Dimensional B—O Chains [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(9): 1550-1559.
[13]	ZHENG Quan, LIU Xuechao, WANG Hao, ZHU Xinfeng, PAN Xiuhong, CHEN Kun, DENG Weijie, TANG Meibo, XU Hao, WU Honghui, JIN Min. Effect of Aluminum Doping on the Crystal Structure and Properties of Indium Selenide Crystals [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(9): 1528-1535.
[14]	WU Miao, SONG Juan, ZHOU Yunlong, REN Chuanqing. Synthesis, Crystal Structure and Fluorescence Properties of Zn(II) Complex Based on Pyrazine Carboxylic Acid Ligand [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(9): 1576-1582.
[15]	AN Hangyi, HUANG Yanxi, WANG Airong, WANG Xiaoli, LI Jiaming, SHI Zhongfeng. A Novel Three-Dimensional Ni (II) Complex: Synthesis, Crystal Structure and Detection for Fe³⁺, CrO^2-₄ and Cr₂O^2-₇ in Water [J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(9): 1599-1607.