Citation: Mei ZHU, Wei-Nan XIE, Mai-E YANG, Feng-Zhen HUA, Guo-Ning ZHANG, Yu-Cheng WANG, Hong ZHAO. One Novel Tetranuclear Copper Cluster by 2-(1H-Pyrazol-3-yl)pyridine: Synthesis, Structure and Properties[J]. Chinese Journal of Structural Chemistry, ;2020, 39(5): 949-954. doi: 10.14102/j.cnki.0254-5861.2011-2523 shu

One Novel Tetranuclear Copper Cluster by 2-(1H-Pyrazol-3-yl)pyridine: Synthesis, Structure and Properties

a.
Institute of Medicinal Biotechnology, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China
b.
School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China

Corresponding author: Yu-Cheng WANG, wangyucheng@imb.pumc.edu.cn
Received Date: 8 July 2019
Accepted Date: 26 November 2019

Fund Project: the Jiangsu Ainaji Neoenergy Science & Technology Co., Ltd. 8507040091the Fundamental Research Funds for the Central Universities 3207045420the National Natural Science Foundation of China 81703366

Figures(6)

A novel tetranuclear copper cluster [Cu₄(μ-L)₆Cl₂] was constructed by 2-(1H-pyrazol-3-yl) pyridine (HL) under hydrothermal conditions, and structurally concluded by single-crystal X-ray diffractions, elemental analyses and IR spectra. The title complex 1 was of triclinic system, space group P\begin{document}$ \overline 1 $\end{document}, C₂₄H₁₈ClCu₂N₉, M_r = 595.01, a = 9.6497(13), b = 11.4133(7), c = 13.0919(15) Å, α = 99.166(7), β = 108.707(11), γ = 111.974(9)^o, V = 1200.7(2) Å³, Z = 2, D_c = 1.997 g/cm³, F(000) = 706, μ(MoKα) = 3.203 mm^-1, R_int = 0.0404, R = 0.0536 and wR = 0.1490 for 4890 observed reflections with I > 2σ(I). In this structure, complex 1 was the unimolecule with unprecedented tetranuclear cluster, which was expanded into a 2D network by wide-ranging C–H···Cl intermolecular hydrogen bonds and further exhibited a 3D supramolecular architecture based on π-π stacking interactions. In addition, the complex was thermally stable up to 300 ℃ and the solid state fluorescent property of 1 was examined and compared with the ligand.
- 2-(1H-pyrazol-3-yl)pyridine,
- tetranuclear copper cluster,
- fluorescent property
1. [1]
  Lu, Y. Z.; Chen, W. Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries. Chem. Soc. Rev. 2012, 41, 3594–3623. doi: 10.1039/c2cs15325d
2. [2]
  Liu, L.; Peng, Y. F.; Lv, X. X.; Li, K.; Li, B. L.; Wu, B. Construction of three coordination polymers based on tetranuclear copper(Ⅱ) clusters: syntheses, structures and photocatalytic properties. CrystEngComm. 2016, 18, 2490–2499. doi: 10.1039/C5CE02492G
3. [3]
  Burrows, A. D.; Mahon, M. F.; Sebestyen, V. M.; Lan, Y. H.; Powell, A. K. Synthesis, structures, and magnetic behavior of new anionic copper(Ⅱ) sulfate aggregates and chains. Inorg. Chem. 2012, 51, 10983–10989. doi: 10.1021/ic301478x
4. [4]
  Zaworotko, M. J. Superstructural diversity in two dimensions: crystal engineering of laminated solids. Chem. Commun. 2001, 1, 1–9.
5. [5]
  Eddaoudi, M.; Moler, D. B.; Li, H. L.; Chen, B. L.; Reineke, T. M.; O'Keeffe, M.; Yaghi, O. M. Modular chemistry: secondary building units as a basis for the design of highly porous and robust metalorganic carboxylate frameworks. Acc. Chem. Res. 2001, 34, 319–330. doi: 10.1021/ar000034b
6. [6]
  Janiak, C. Engineering coordination polymers towards applications. Dalton Trans. 2003, 14, 2781–2804.
7. [7]
  Braña, E.; Quiñone, D.; Martínez, S.; Grassi, J.; Carrera, I.; Torres, J.; González-Platas, J.; Seoane, G.; Kremer, C.; Mendoza, C. New polynuclear compounds based on N-benzyliminodipropionic acid: solution studies, synthesis, and X-ray crystal structures. J. Coord. Chem. 2016, 69, 3650–3663. doi: 10.1080/00958972.2016.1239086
8. [8]
  Ben Salah, A. M.; Naïli, H.; Arczyn´ski, M.; Fitta, M. 0D and 1D copper(Ⅱ) coordination polymers based on 2-methyl-1H-imidazole: structural, vibrational and magnetic characterizations. J. Organomet. Chem. 2016, 805, 42–48. doi: 10.1016/j.jorganchem.2016.01.010
9. [9]
  Zienkiewicz-Machnik, M.; Masternak, J.; Kazimierczuk, K.; Barszcz, B. Structural analysis and physico-chemical characterization of mononuclear manganese(Ⅱ) and polynuclear copper(Ⅱ) complexes with pyridine-based alcohol. J. Mol. Struct. 2016, 1126, 37–46. doi: 10.1016/j.molstruc.2016.01.082
10. [10]
  Maity, D. K.; Bhattacharya, B.; Mondal, R.; Ghoshal, D. Five diverse bivalent metal coordination polymers based on benzene dicarboxylate and bent dipyridyl ligands: syntheses, structures, and photoluminescent properties. CrystEngComm. 2014, 16, 8896–8909. doi: 10.1039/C4CE00966E
11. [11]
  Madhu, V.; Das, S. K. Neutral coordination polymers based on a metal-mono(dithiolene) complex: synthesis, crystal structure and supramolecular chemistry of [Zn(dmit)(4, 4΄-bpy)]_n, [Zn(dmit)(4, 4΄-bpe)]_n and [Zn(dmit)(bix)]_n (4, 4΄-bpy = 4, 4΄-bipyridine, 4, 4΄-bpe = trans-1, 2-bis(4-pyridyl)ethene, bix = 1, 4-bis(imidazole-1-ylmethyl)-benzene). Dalton Trans. 2011, 40, 12901–12908. doi: 10.1039/c1dt10814j
12. [12]
  Liu, G. X.; Xu, H.; Zhou, H.; Nishihara, S.; Ren, X. M. Temperature-induced assembly of MOF polymorphs: syntheses, structures and physical properties. CrystEngComm. 2012, 14, 1856–1864. doi: 10.1039/c1ce05369h
13. [13]
  Fang, H. C.; Zhu, J. Q.; Zhou, L. J.; Jia, H. Y.; Li, S. S.; Gong, X.; Li, S. B.; Cai, Y. P.; Thallapally, P. K.; Liu, J.; Exarhos, G. J. pH-Dependent assembly and conversions of six cadmium(Ⅱ)-based coordination complexes. Cryst. Growth Des. 2010, 10, 3277–3284. doi: 10.1021/cg1004598
14. [14]
  Tang, J.; Costa, J. S.; Golobicˇ, A.; Kozlevcˇar, B.; Robertazzi, A.; Vargiu, A. V.; Gamez, P.; Reedijk, J. Magnetic coupling between copper(Ⅱ) ions mediated by hydrogen-bonded (neutral) water molecules. Inorg. Chem. 2009, 48, 5473–5479. doi: 10.1021/ic900507w
15. [15]
  Zou, R. Q.; Bu, X. H.; Du, M.; Sui, Y. X. A hydrogen-bonded 3D coordination network of Cu^Ⅱ nitrate with pyridine-2, 6-dicarboxylic acid and 3-(2-pyridyl)pyrazole: hydrothermal synthesis, characterization and crystal structure. J. Mol. Struct. 2004, 707, 11–15. doi: 10.1016/j.molstruc.2004.05.001
16. [16]
  Fang, S. M.; Sañudo, E. C.; Hu, M.; Zhang, Q.; Zhou, L. M.; Liu, C. S. Copper(Ⅱ) complexes with cis-epoxysuccinate ligand: syntheses, crystal structures, and magnetic properties. Aust. J. Chem. 2011, 64, 217–226. doi: 10.1071/CH10371
17. [17]
  Wei, P. H.; Wu, X. Y.; Fan, L. M.; Li, D. C.; Zhang, X. T.; Dou, J. M.; Liu, X. Z.; Shi, C. W. Hydrothermal synthesis and crystal structure of one novel 1-D copper(Ⅱ)-organic framework: {[Cu₂(PP)₂(CBPC)]₂·7H₂O}_n. Chin. J. Struct. Chem. 2010, 12, 1774–1779.
18. [18]
  Fan, L. M.; Li, D. C.; Wei, P. H.; Zhang, X. T.; Dou, J. M. Synthesis, structure, and magnetic property of one snake-shaped copper(Ⅱ)-organic compound: Cu[Cu₂(PP)₂](CBPC)₂]·2(H₂O). Chin. J. Struct. Chem. 2011, 10, 1381–1386.
19. [19]
  Ardizzoia, G. A.; Brenna, S. Hydroxo-bridged copper(Ⅱ) cubane complexes, Coord. Chem. Rev. 2016, 311, 53–74. doi: 10.1016/j.ccr.2015.11.013
20. [20]
  Bikas, R.; Hosseini-Monfared, H.; Korabik, M.; Krawczyk, M. S.; Lis, T. Synthesis, structure and magnetic properties of a 1D coordination polymer of Cu(Ⅱ) containing phenoxido and dicyanamido bridging groups. Polyhedron 2014, 81, 282–289. doi: 10.1016/j.poly.2014.06.024
21. [21]
  Hickey, J. L.; Donnelly, P. S.; Diagnostic imaging of Alzheimer's disease with copper and technetium complexes. Coord. Chem. Rev. 2012, 256, 2367–2380. doi: 10.1016/j.ccr.2012.03.035
22. [22]
  Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 3–8. doi: 10.1107/S2053229614024218
23. [23]
  Isaac, J. A.; Mansour, A. T.; David, R.; Kochem, A.; Philouze, C.; Demeshko, S.; Meyer, F.; Réglier, M.; Simaan, A. J.; Caldarelli, S.; Yemloul, M.; Jamet, H.; Thibon-Pourret, A.; Belle, C. Tetranuclear and dinuclear phenoxido bridged copper complexes based on unsymmetrical thiosemicarbazone ligands. Dalton Trans. 2018, 47, 9665–9676. doi: 10.1039/C8DT02452A
24. [24]
  Klingele (n´ee Hausmann), J.; Prikhod'ko, A. I.; Leibeling, G.; Demeshko, S.; Dechert, S.; Meyer, F. Pyrazolate-based copper(Ⅱ) and nickel(Ⅱ) [2 × 2] grid complexes: protonation-dependent self-assembly, structures and properties. Dalton Trans. 2007, 2003–2013.
25. [25]
  Lv, X. X.; Shi, L. L.; Li, K.; Li, B. L.; Li, H. Y. An unusual porous cationic metal-organic framework based on a tetranuclear hydroxyl-copper(Ⅱ) cluster for fast and highly efficient dichromate trapping through a single-crystal to single-crystal process. Chem. Commun. 2017, 53, 1860–1867. doi: 10.1039/C6CC09676J
26. [26]
  Ma, Y. S.; Yang, Z.; Cai, W. S.; Tang, X. Y.; Yuan, R. X. Assembly of 1-D and decanuclear cage compounds from copper halide, cyclohexenephosphonic acid, and 3-(2-pyridyl)pyrazole. J. Coord. Chem. 2015, 68, 1633–1643. doi: 10.1080/00958972.2015.1021342
27. [27]
  Cheng, Z. Y.; Hu, H. P.; Yang, J. P.; Qiu, X. J.; Wang, C. X.; Ji, G. F. Synthesis, structure and DFT calculations of a novel copper(Ⅱ) complex based on tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate. Chin. J. Struct. Chem. 2017, 36, 795–804.
28. [28]
  Batool, S. S.; Gilani, S. R.; Tahir, M. N.; Harrison, W. T. A.; Mitu, L.; Mazharr, S. Synthesis and structural features of copper(Ⅱ) complexes of N, N, N΄, N΄-tetramethylethylenediamine with 2-chlorobenzoate¹⁻ and 2-hydroxybenzoate¹⁻. J. Coord. Chem. 2018, 71, 2569–2583. doi: 10.1080/00958972.2018.1503653
29. [29]
  Li, C. H.; Li, W.; Li, H. F.; Tan, X. W. Crystal structure, fluorescence and thermal stability properties of a dinuclear copper(Ⅱ) complex [Cu₂(L)₂(phen)₂]·5H₂O (H₂L = bicycle[2.2. 1]hept-2-en-5, 6-dicarboxylic acid). Chin. J. Struct. Chem. 2015, 12, 1922–1926.
30. [30]
  Cui, Y. J.; Yue, Y. F.; Qian, G. D.; Chen, B. L. Luminescent functional metal-organic frameworks. Chem. Rev. 2012, 112, 1126–1162. doi: 10.1021/cr200101d
1. [1]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
2. [2]
  Fahui Xiang , Lu Li , Zhen Yuan , Wuji Wei , Xiaoqing Zheng , Shimin Chen , Yisi Yang , Liangji Chen , Zizhu Yao , Jianwei Fu , Zhangjing Zhang , Shengchang Xiang . Enhanced C₂H₂/CO₂ separation in tetranuclear Cu(Ⅱ) cluster-based metal-organic frameworks by adjusting divider length of pore space partition. Chinese Chemical Letters, 2025, 36(3): 109672-. doi: 10.1016/j.cclet.2024.109672
3. [3]
  Haiming Wu , Gaya N. Andrew , Rajini Anumula , Zhixun Luo . Corrigendum to 'How ligand coordination and superatomic-states accommodate the structure and property of a metal cluster: Cu₄ (dppy)₄ Cl₂ vs. Cu₂₁ (dppy)₁₀ with altered photoluminescence' [Chin. Chem. Lett. 35 (2024) 108340]. Chinese Chemical Letters, 2024, 35(12): 109912-. doi: 10.1016/j.cclet.2024.109912
4. [4]
  Tian TIAN , Meng ZHOU , Jiale WEI , Yize LIU , Yifan MO , Yuhan YE , Wenzhi JIA , Bin HE . Ru-doped Co₃O₄/reduced graphene oxide: Preparation and electrocatalytic oxygen evolution property. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 385-394. doi: 10.11862/CJIC.20240298
5. [5]
  Zhijia Zhang , Shihao Sun , Yuefang Chen , Yanhao Wei , Mengmeng Zhang , Chunsheng Li , Yan Sun , Shaofei Zhang , Yong Jiang . Epitaxial growth of Cu_2-xSe on Cu (220) crystal plane as high property anode for sodium storage. Chinese Chemical Letters, 2024, 35(7): 108922-. doi: 10.1016/j.cclet.2023.108922
6. [6]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
7. [7]
  Yuan ZHU , Xiaoda ZHANG , Shasha WANG , Peng WEI , Tao YI . Conditionally restricted fluorescent probe for Fe³⁺ and Cu²⁺ based on the naphthalimide structure. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 183-192. doi: 10.11862/CJIC.20240232
8. [8]
  Yudi Cheng , Xiao Wang , Jiao Chen , Zihan Zhang , Jiadong Ou , Mengyao She , Fulin Chen , Jianli Li . A near-infrared fluorescent probe for visualizing transformation pathway of Cys/Hcy and H₂S and its applications in living system. Chinese Chemical Letters, 2024, 35(5): 109156-. doi: 10.1016/j.cclet.2023.109156
9. [9]
  He Yao , Wenhao Ji , Yi Feng , Chunbo Qian , Chengguang Yue , Yue Wang , Shouying Huang , Mei-Yan Wang , Xinbin Ma . Copper-catalyzed and biphosphine ligand controlled 3,4-boracarboxylation of 1,3-dienes with carbon dioxide. Chinese Chemical Letters, 2025, 36(4): 110076-. doi: 10.1016/j.cclet.2024.110076
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]
  Xin Li , Zhen Xu , Donglei Bu , Jinming Cai , Huamei Chen , Qi Chen , Ting Chen , Fang Cheng , Lifeng Chi , Wenjie Dong , Zhenchao Dong , Shixuan Du , Qitang Fan , Xing Fan , Qiang Fu , Song Gao , Jing Guo , Weijun Guo , Yang He , Shimin Hou , Ying Jiang , Huihui Kong , Baojun Li , Dengyuan Li , Jie Li , Qing Li , Ruoning Li , Shuying Li , Yuxuan Lin , Mengxi Liu , Peinian Liu , Yanyan Liu , Jingtao Lü , Chuanxu Ma , Haoyang Pan , JinLiang Pan , Minghu Pan , Xiaohui Qiu , Ziyong Shen , Qiang Sun , Shijing Tan , Bing Wang , Dong Wang , Li Wang , Lili Wang , Tao Wang , Xiang Wang , Xingyue Wang , Xueyan Wang , Yansong Wang , Yu Wang , Kai Wu , Wei Xu , Na Xue , Linghao Yan , Fan Yang , Zhiyong Yang , Chi Zhang , Xue Zhang , Yang Zhang , Yao Zhang , Xiong Zhou , Junfa Zhu , Yajie Zhang , Feixue Gao , Li Wang . Recent progress on surface chemistry Ⅱ: Property and characterization. Chinese Chemical Letters, 2025, 36(1): 110100-. doi: 10.1016/j.cclet.2024.110100
12. [12]
  Shuwen SUN , Gaofeng WANG . Design and synthesis of a Zn(Ⅱ)-based coordination polymer as a fluorescent probe for trace monitoring 2, 4, 6-trinitrophenol. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 753-760. doi: 10.11862/CJIC.20240399
13. [13]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057
14. [14]
  Junying LI , Xinyan CHEN , Xihui DIAO , Muhammad Yaseen , Chao CHEN , Hao WANG , Chuansong QI , Wei LI . Chiral fluorescent sensor Tb³⁺@Cd-CP based on camphoric acid for the enantioselective recognition of R- and S-propylene glycol. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2497-2504. doi: 10.11862/CJIC.20240084
15. [15]
  Jiao Chen , Zihan Zhang , Guojin Sun , Yudi Cheng , Aihua Wu , Zefan Wang , Wenwen Jiang , Fulin Chen , Xiuying Xie , Jianli Li . Benzo[4,5]imidazo[1,2-a]pyrimidine-based structure-inherent targeting fluorescent sensor for imaging lysosomal viscosity and diagnosis of lysosomal storage disorders. Chinese Chemical Letters, 2024, 35(11): 110050-. doi: 10.1016/j.cclet.2024.110050
16. [16]
  Wei-Tao Dou , Qing-Wen Zeng , Yan Kang , Haidong Jia , Yulian Niu , Jinglong Wang , Lin Xu . Construction and application of multicomponent fluorescent droplets. Chinese Chemical Letters, 2025, 36(1): 109995-. doi: 10.1016/j.cclet.2024.109995
17. [17]
  Guang Xu , Cuiju Zhu , Xiang Li , Kexin Zhu , Hao Xu . Copper-catalyzed asymmetric [4+1] annulation of yne–allylic esters with pyrazolones. Chinese Chemical Letters, 2025, 36(4): 110114-. doi: 10.1016/j.cclet.2024.110114
18. [18]
  Qi Li , Zi-Lu Wang , Yun-He Xu . Copper-catalyzed 1,4-silylcyanation of 1,3-enynes: A silyl radical-initiated approach for synthesis of difunctionalized allenes. Chinese Chemical Letters, 2025, 36(3): 109991-. doi: 10.1016/j.cclet.2024.109991
19. [19]
  Ze-Yuan Ma , Mei Xiao , Cheng-Kun Li , Adedamola Shoberu , Jian-Ping Zou . S-(1,3-Dioxoisoindolin-2-yl)O,O-diethyl phosphorothioate (SDDP): A practical electrophilic reagent for the phosphorothiolation of electron-rich compounds. Chinese Chemical Letters, 2024, 35(5): 109076-. doi: 10.1016/j.cclet.2023.109076
20. [20]
  Hao Cai , Xiaoyan Wu , Lei Jiang , Feng Yu , Yuxiang Yang , Yan Li , Xian Zhang , Jian Liu , Zijian Li , Hong Bi . Lysosome-targeted carbon dots with a light-controlled nitric oxide releasing property for enhanced photodynamic therapy. Chinese Chemical Letters, 2024, 35(4): 108946-. doi: 10.1016/j.cclet.2023.108946

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(289)
HTML views(5)

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