Citation: Xin ZHANG, Xiao-Feng JIANG, Yun-Zhou CHEN, Yun-Feng CHEN, Li-Li DING, Li-Hui JIA. A Double Azole-bridged Dinuclear Copper(Ⅱ) Complex Containing 4-Pyridyl-NH-1, 2, 3-triazoles: Synthesis, Structure and Magnetism[J]. Chinese Journal of Structural Chemistry, ;2020, 39(5): 918-926. doi: 10.14102/j.cnki.0254-5861.2011-2595 shu

A Double Azole-bridged Dinuclear Copper(Ⅱ) Complex Containing 4-Pyridyl-NH-1, 2, 3-triazoles: Synthesis, Structure and Magnetism

Xin ZHANG ^a ,
Xiao-Feng JIANG ^a ,
Yun-Zhou CHEN ^a ,
Yun-Feng CHEN ^a ,
Li-Li DING ^a,, ,
Li-Hui JIA ^{a, b,,}

a.
Key Laboratory for Green Chemistry Process of Ministry of Education, School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan 430073, China
b.
Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Function Molecules, Hubei University, Wuhan 430062, China

Corresponding author: Li-Li DING, 7384419@qq.com Li-Hui JIA, jialihui715@wit.edu.cn
Received Date: 5 September 2019
Accepted Date: 21 November 2019

Fund Project: the National Natural Science Foundation of China 21002076the National Natural Science Foundation of China 21441007the Open Fund Project of Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Function Molecules, Hubei University KLSAOFM1709the Graduate Innovative Fund of Wuhan Institute of Technology CX2018150the Graduate Innovative Fund of Wuhan Institute of Technology CX2018132

Figures(4)

A new dinuclear copper(Ⅱ) compound [Cu₂(CH₃COO)₂(L)₂(H₂O)₂]·4H₂O (1, HL = 4-pyridyl-NH-1, 2, 3-triazole) has been synthesized and characterized. Single-crystal X-ray diffraction showed that complex 1 crystallizes in monoclinic space group P2₁/c with a = 0.8427(1), b = 1.0981(1), c = 1.3610(1) nm, β = 93.364(4)°, V = 1.2573(1) nm³, M_r = 643.56, Z = 2, D_c = 1.700 g/cm³, μ = 1.760 mm^-1, R = 0.0376, wR = 0.0981, and possesses a planar Cu₂N₄ six-membered ring, in which both Cu(Ⅱ) ions are bridged by two 1, 2, 3-triazole ligands. The neighboring dinuclear molecules are bound by strong intermolecular hydrogen bonds to create 1-D chains expanding along the b axis, which further form a 3-D supramolecular framework. Magnetic susceptibility measurement indicated the presence of weak antiferromagnetic interactions within the complex. The best fit using spin Hamiltonian yields the magnetic coupling constant J = –14.82 cm^-1 above 30 K. The magnetic data are compared to those obtained for related double diazine bridged dinuclear copper(Ⅱ) complexes and magneto-structural correlations are discussed.
- dinuclear Cu(Ⅱ) complexes,
- 4-pyridyl-NH-1,2,3-triazole,
- magnetic properties,
- magneto-structural correlation
1. [1]
  Chen, Y. Z.; Chen, X. L.; Chen, Y. F.; Jia, L. H.; Zeng, M. H. Design, structure and magnetic properties of a novel one dimensional Mn(Ⅱ) coordination polymer constructed from 4-pyridyl-NH-1, 2, 3-triazole. Inorg. Chem. Comm. 2017, 84, 182–185. doi: 10.1016/j.inoche.2017.08.012
2. [2]
  a) Ranga, M. R. R.; Romanova, J.; Curry, R. J.; Silva, S. R. P.; Jarowski, P. D. The role of substituent effects in tuning metallophilic interactions and emission energy of bis-4-(2-pyridyl)-1, 2, 3-triazolatoplatinum(Ⅱ) complexes. Angew. Chem. Int. Ed. 2015, 54, 7949–7953; b) Romanova, J.; Prabhath, M. R. R.; Jarowski, P. D. Relationship between metallophilic interactions and luminescent properties in Pt(Ⅱ) complexes: TD-DFT guide for the molecular design of light-responsive materials. J. Phys. Chem. C 2016, 120, 2002–2012. c) Wang, D.; Denux, D.; Ruiz, J.; Astrucl, D. The clicked pyridyl-triazole ligand: from homogeneous to robust, recyclable heterogeneous mono-and polymetallic palladium catalysts for efficient Suzuki-Miyaura, Sonogashira, and Heck reactions. Adv. Synth. Catal. 2013, 355, 129–142.
3. [3]
  a) Crowley, J. D.; Preston, D.; Van Hilst, Q. V.; Crowley, J. D. Functional metal complexes from CuAAC "click" bidentate and tridentate pyridyl-1, 2, 3-triazole ligands. Dalton Trans. 2018, 47, 997–1002; b) Meldal, M.; Tornoe, C. W. Cu-Catalyzed azide-alkyne cycloaddition. Chem. Rev. 2008, 108, 2952–3015. c) Liang, L.; Astruc, D. The copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) "click" reaction and its applications. An overview. Coord. Chem. Rev. 2011, 255, 2933–2945; d) Hein, J. E.; Fokin, V. V. Copper-catalyzed azid-alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(I) acetylidesw. Chem. Soc. Rev. 2010, 39, 1302–1315.
4. [4]
  a) Crowley, J. D.; McMorran, D. A. "Click-triazole" coordination chemistry: exploiting 1, 4-disubstituted-1, 2, 3-triazoles as ligands. Top. Heterocycl. Chem. 2012, 28, 31–84; b) Struthers, H.; Mindt, T. L.; Schibli, R. Metal chelating systems synthesized using the copper(I) catalyzed azide-alkyne cycloaddition. Dalton Trans. 2010, 39, 675–696. c) Vasdev, R. A. S.; Preston, D.; Crowley, J. D. Functional metallosupramolecular architectures using 1, 2, 3-triazole ligands: it's as easy as 1, 2, 3 "click". Dalton Trans. 2017, 46, 2402–2414. d) Schweinfurth, D.; Hettmanczyk, L.; Suntrup, L.; Sarkar, B. Metal complexes of click-derived triazoles and mesoionic carbenes: electron transfer, photochemistry, magnetic bistability, and catalysis. Z. Anorg. Allg. Chem. 2017, 643, 554–584.
5. [5]
  Hu, T. L.; Li, J. R.; Liu, C. S. Syntheses, crystal structures, and magneto-structural correlations of Novel Cu^Ⅱ complexes containing a planar [Cu(µ-L¹)]₂ (HL¹ = 3-(2-pyridyl)pyrazole) unit: from dinuclear to tetranuclear and then to one-dimensional compounds. Inorg. Chem. 2006, 45, 162−173. doi: 10.1021/ic051488d
6. [6]
  Mokuolu, Q. F.; Foguet-Albiol, D.; Jones, L. F.; Wolowska, J.; Kowalczyk, R. M.; Kilne, C. A.; Christou, G.; McGowan, P. C.; Halcrow, M. A. Four copper(Ⅱ) pyrazolido complexes derived from reactions of 3{5}-substituted pyrazoles with CuF₂ or Cu(OH)₂. Dalton Trans. 2007, 14, 1392−1399.
7. [7]
  Du, M.; Chen, S. T.; Guo, Y. M.; Bu, X. H.; Ribas, J. Synthesis, crystal structure, spectroscopy and magnetic properties of a dinuclear Cu^Ⅱ complex with 3, 5-bis(2-pyridyl)pyrazole bridging ligand. J. Mol. Struct. 2005, 737, 17−21. doi: 10.1016/j.molstruc.2004.10.005
8. [8]
  a) Pons, J.; López, X.; Casabó, J.; Miravitlles, C. Copper complexes with a pyrazole derivative ligand. Crystal structure of tetrakis{[(3, 5-bis(pyridin-2-yl)pyrazolate)-(aqua)copper(Ⅱ)] nitrate monohydrate}. Inorg. Chim. Acta 1992, 195, 61−66. b) Munakata, M.; Wu, L. P.; Yamamoto, M.; Kuroda-Sowa, W.; Maekawa, M.; Kawata, S.; Kitagawa, S. J. Chem. Soc. Dalton Trans. 1995, 24, 4099−4106.
9. [9]
  Slangen, P. M.; van Koningsbruggen. P. J.; Goubitz, K.; Haasnoot, J. G. Isotropic magnetic exchange interaction through double u-1, 2, 4-triazolato-N1, N2 bridges: X-ray crystal structure, magnetic properties, and EPR study of bis(u-3-pyridin-2-yl-l, 2, 4-triazolato-N΄, N1, N2)(sulfato-o)aquacopper(Ⅱ)diaquacopper(Ⅱ) trihydra. Inorg. Chem. 1994, 33, 1121–1126. doi: 10.1021/ic00084a025
10. [10]
  Prins, R.; Birker, P. J. M. W. L.; Haasnoot, J. G.; Verschoor, G. C.; Reedijk, J. Magnetic properties of dimeric disubstituted-triazole copper(Ⅱ) compounds. X-ray structure of bis[u-3, 5-bis(pyridin-2-yl)-1, 2, 4-triazolato-N', N1, N2, N"]-bis[aqua(trifluoromethanesulfonato-O)copper(Ⅱ)]. J. Inorg. Chem. 1985, 24, 4128–4133. doi: 10.1021/ic00218a031
11. [11]
  Kaase, D.; Gotzmann, C.; Rein, S.; Lan, Y. H.; Kacprzak, S.; Klingele, J. [1, 2, 4]Triazolo[4, 3-a]pyridines as bridging ligands magnetism of azole-bridged dinuclear copper(Ⅱ) complexes influenced by the trigonal distortion parameter τ. J. Inorg. Chem. 2014, 53, 5546–5555. doi: 10.1021/ic500226z
12. [12]
  Bai, S. Q.; Jiang, L.; Zuo, J. L.; Yan, C. H.; Hor, T. S. A. Dinuclear Cu(Ⅱ) 1, 2, 3-triazole-bridged complex with ferromagnetic coupling. Aust. J. Chem. 2013, 66, 1029–1033. doi: 10.1071/CH13224
13. [13]
  Guha, P. M.; Phan, H.; Kinyon, J. S.; Brotherton, W. S.; Sreenath, W.; Simmons, J. T.; Wang. Z. X.; Clark, R. J.; Dalal, N. S.; Shatruk, M.; Zhu, L. Structurally diverse copper(Ⅱ) complexes of polyaza ligands containing 1, 2, 3-triazoles: site selectivity andmagnetic properties. Inorg. Chem. 2012, 51, 3465−3477. doi: 10.1021/ic2021319
14. [14]
  Hu, Q. Q.; Liu, Y.; Deng, X. X.; Li, Y. J.; Chen, Y. F. Aluminium(Ⅲ) chloride-catalyzed three-component condensation of aromatic aldehydes, nitroalkanes and sodium azide for the synthesis of 4-aryl-NH-1, 2, 3-triazoles. Adv. Synth. Catal. 2016, 358, 1689–1693. doi: 10.1002/adsc.201600098
15. [15]
  a) Sheldrick, G. M. A short history of SHELX. Acta. Cryst. 2008, A64, 112–122. b) Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta. Cryst. 2015, C71, 3–8. c) Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howad, J. A. K.; Puschmann, M. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. 2009, 42, 339–341
16. [16]
  Addison, A. W.; Rao, T. N.; Reedijk, J.; Rijin, J. V.; Verschoor, G. C. Synthesis, structure, and spectroscopicproperties of copper(Ⅱ) compounds containing nitrogen-sulphur donor ligands; the crystal and molecular structure of aqua[l, 7-bis(N-methylbenzimidazol-2΄-yl)-2, 6-dithiaheptane]copper(Ⅱ) perchlorate. J. Chem. Soc. Dalton Trans. 1984, 7, 1349–1356.
17. [17]
  Janiak, C. A critical account on π-π stacking in metal complexes with aromatic nitrogen-containing ligand. J. Chem. Soc. Dalton Trans. 2000, 8, 3885–3896.
18. [18]
  Kahn, O. Molecular Magnetism. New York: VCH 1993.
19. [19]
  Chilton, N. F.; Anderson, R. P.; Turner, L. D.; Soncini, A.; Murray, K. S. PHI: a powerful new program for the analysis of anisotropic monomeric and exchange-coupled polynuclear d-and f-block complexes. J. Comput. Chem. 2013, 34, 1164–1175. doi: 10.1002/jcc.23234
20. [20]
  Li, Y. X.; Chen, Y. Z.; Liu, Y.; Jia, L. H.; Chen, Y. F. Three copper(Ⅱ) complexes constructed from 4-(2-pyridyl)-1H-1, 2, 3-triazole ligands: syntheses, structures, optical, and electrochemical properties. Transit. Met. Chem. 2018, 43, 731–737. doi: 10.1007/s11243-018-0261-1
21. [21]
  Zhang, Y.; Chen, Y. Z.; Zhou, S. L.; Meng, X. G.; Jia, L. H.; Chen, Y. F. Synthesis, structure and properties of a new NH-1, 2, 3-triazole based octanuclear copper(Ⅱ) complex. Inorg. Chem. Commun. 2017, 84, 159–163. doi: 10.1016/j.inoche.2017.08.008
22. [22]
  Lei, X.; Chen, Y. Z.; Li, Y. X.; Jia, L. H.; Chen, Y. F. Two mono-and binuclear Zn(Ⅱ) coordination complexes containing 4-pyridyl-NH-1, 2, 3-triazole ligand: syntheses, structures and photoluminescence properties. Chin. J. Inorg. Chem. 2018, 34, 545–550
1. [1]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
2. [2]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
3. [3]
  Yanfen PENG , Xinyue WANG , Tianbao LIU , Xiaoshuo WU , Yujing WEI . Syntheses and luminescence of four Cd(Ⅱ)/Zn(Ⅱ) complexes constructed by 1,3‐bis(4H‐1,2,4‐triazole)benzene. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1416-1426. doi: 10.11862/CJIC.20250018
4. [4]
  Jiajia Zhuang , Chunyu Cui , Changjiang Li , Gang Luo , Jiaping Tong , Di Sun . Counter-ion effect to the Ising-type magnetic anisotropy and magnetic relaxation in trigonal bipyramidal Co(Ⅱ) complexes. Chinese Chemical Letters, 2025, 36(7): 110091-. doi: 10.1016/j.cclet.2024.110091
5. [5]
  Yadan SUN , Xinfeng LI , Qiang LIU , Oshio Hiroki , Yinshan MENG . Structures and magnetism of dinuclear Co complexes based on imine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2212-2220. doi: 10.11862/CJIC.20240131
6. [6]
  Shengwen Guan , Zhaotong Wei , Ningxu Han , Yude Wei , Bin Xu , Ming Wang , Junjuan Shi . Construction of metallo-complexes with 2,2′:6′,2″-terpyridine substituted triphenylamine in different modified positions and their photophysical properties. Chinese Chemical Letters, 2024, 35(7): 109348-. doi: 10.1016/j.cclet.2023.109348
7. [7]
  Ya-Xuan Xue , Han Xu , Jia-Nan Chen , Hai-Quan Tian , Tao Jia , Wei-Dong Liu , Chong-Yang Li , La-Sheng Long , Lan-Sun Zheng , Xiang-Jian Kong . Chiral Ln3Co5 clusters with geometry-dependent chiroptical and magneto-optical properties. Chinese Journal of Structural Chemistry, 2026, 45(1): 100764-100764. doi: 10.1016/j.cjsc.2025.100764
8. [8]
  Xiaxia LIU , Xiaofang MA , Luxia GUO , Xianda HAN , Sisi FENG . Structure and magnetic properties of Mn(Ⅱ) coordination polymers regulated by N-auxiliary ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 587-596. doi: 10.11862/CJIC.20240269
9. [9]
  Zhinan GUO , Junli WANG , Qiang ZHAO , Zhifang JIA , Zuopeng LI , Kewei WANG , Yong GUO . Cu₂O/Bi₂CrO₆ Z-scheme heterojunction: Construction and photocatalytic degradation properties for tetracycline. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 741-752. doi: 10.11862/CJIC.20240403
10. [10]
  Gaofeng WANG , Shuwen SUN , Yanfei ZHAO , Lixin MENG , Bohui WEI . Structural diversity and luminescence properties of three zinc coordination polymers based on bis(4-(1H-imidazol-1-yl)phenyl)methanone. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 849-856. doi: 10.11862/CJIC.20230479
11. [11]
  Zihe SONG , Jinjin ZHAO , Ning REN , Jianjun ZHANG . Crystal structure, thermal analysis, and luminescence properties of six heterocyclic lanthanide complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 181-192. doi: 10.11862/CJIC.20250126
12. [12]
  Jia JI , Zhaoyang GUO , Wenni LEI , Jiawei ZHENG , Haorong QIN , Jiahong YAN , Yinling HOU , Xiaoyan XIN , Wenmin WANG . Two dinuclear Gd(Ⅲ)-based complexes constructed by a multidentate diacylhydrazone ligand: Crystal structure, magnetocaloric effect, and biological activity. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 761-772. doi: 10.11862/CJIC.20240344
13. [13]
  Wanpeng Zhou , Xuwen Da , Yunli Xu , Yatong Peng , Xiulian Liu , Yao Wu , Yu Shi , Aifeng Wu , Yishan Yao , Xuesong Wang , Qianxiong Zhou . HClO-responsive dinuclear Ru(Ⅱ) complexes for selective imaging and efficient photo-inactivation of intracellular bacteria. Chinese Chemical Letters, 2025, 36(6): 110376-. doi: 10.1016/j.cclet.2024.110376
14. [14]
  Wen-Jie Xu , Qian-Cheng Luo , Yang Fang , Chen-Jie Yuan , Jin-Tao Lu , Yuan-Qi Zhai , Yu Wang , Yan-Zhen Zheng . Pseudo-mono-coordinate dysprosium(Ⅲ)-alkoxide complexes exhibit enhanced magnetic axiality and blocking temperature. Chinese Chemical Letters, 2026, 37(7): 110975-. doi: 10.1016/j.cclet.2025.110975
15. [15]
  Ke-Lin Zhu , Zhi-Ao Li , Jiaqi Liang , Yong He , Han-Yuan Gong . Atropisomeric carbon-rich macrocycles: Synthesis, structural evolution, and properties. Chinese Chemical Letters, 2026, 37(2): 111629-. doi: 10.1016/j.cclet.2025.111629
16. [16]
  Weichen WANG , Chunhua GONG , Junyong ZHANG , Yanfeng BI , Hao XU , Jingli XIE . Construction of two metal-organic frameworks by rigid bis(triazole) and carboxylate mixed-ligands and their catalytic properties for CO₂ cycloaddition reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1377-1386. doi: 10.11862/CJIC.20230415
17. [17]
  Zhao-Bo Hu , Ling-Ao Gui , Long-He Li , Tong-Tong Xiao , Adam T. Hand , Pagnareach Tin , Mykhaylo Ozerov , Yan Peng , Zhongwen Ouyang , Zhenxing Wang , Zi-Ling Xue , You Song . Co^Ⅱ single-ion magnet and its multi-dimensional aggregations: Influence of the structural rigidity on magnetic relaxation process. Chinese Chemical Letters, 2025, 36(2): 109600-. doi: 10.1016/j.cclet.2024.109600
18. [18]
  Hongyu Tang , Dongming Liu , Jinfu Huang , Liang Zhang , Yang Tang , Bin Huang , Yanwei Li , Shunhua Xiao , Yiling Sun , Renheng Wang . Excellent structural stability and electrochemical properties of LiNi_0.9Co_0.05Mn_0.05O₂ material by surface Ni²⁺ anchoring and Cs⁺ doping. Chinese Chemical Letters, 2025, 36(6): 109987-. doi: 10.1016/j.cclet.2024.109987
19. [19]
  Xiaoling WANG , Hongwu ZHANG , Daofu LIU . Synthesis, structure, and magnetic property of a cobalt(Ⅱ) complex based on pyridyl-substituted imino nitroxide radical. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 407-412. doi: 10.11862/CJIC.20240214
20. [20]
  Na Wang , Hongzhi Hu , Qiangqiang Jia , Yang Liu , Zunqi Liu , Dawei Fu . Halogen-substitution-induced magnetic-phase transition photoelectric synergy in L-valine crown ether inclusion complexes. Chinese Chemical Letters, 2026, 37(10): 111530-. doi: 10.1016/j.cclet.2025.111530

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(1708)
HTML views(68)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142