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]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  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
7. [7]
  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
8. [8]
  Ziyi Liu , Xunying Liu , Lubing Qin , Haozheng Chen , Ruikai Li , Zhenghua Tang . Alkynyl ligand for preparing atomically precise metal nanoclusters: Structure enrichment, property regulation, and functionality enhancement. Chinese Journal of Structural Chemistry, 2024, 43(11): 100405-100405. doi: 10.1016/j.cjsc.2024.100405
9. [9]
  Hanqing Zhang , Xiaoxia Wang , Chen Chen , Xianfeng Yang , Chungli Dong , Yucheng Huang , Xiaoliang Zhao , Dongjiang Yang . Selective CO2-to-formic acid electrochemical conversion by modulating electronic environment of copper phthalocyanine with defective graphene. Chinese Journal of Structural Chemistry, 2023, 42(10): 100089-100089. doi: 10.1016/j.cjsc.2023.100089
10. [10]
  Yu-Yu Tan , Lin-Heng He , Wei-Min He . Copper-mediated assembly of SO₂F group via radical fluorine-atom transfer strategy. Chinese Chemical Letters, 2024, 35(9): 109986-. doi: 10.1016/j.cclet.2024.109986
11. [11]
  Yuxiang Zhang , Jia Zhao , Sen Lin . Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100415-100415. doi: 10.1016/j.cjsc.2024.100415
12. [12]
  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
13. [13]
  Wenyi Mei , Lijuan Xie , Xiaodong Zhang , Cunjian Shi , Fengzhi Wang , Qiqi Fu , Zhenjiang Zhao , Honglin Li , Yufang Xu , Zhuo Chen . Design, synthesis and biological evaluation of fluorescent derivatives of ursolic acid in living cells. Chinese Chemical Letters, 2024, 35(5): 108825-. doi: 10.1016/j.cclet.2023.108825
14. [14]
  Chuan-Zhi Ni , Ruo-Ming Li , Fang-Qi Zhang , Qu-Ao-Wei Li , Yuan-Yuan Zhu , Jie Zeng , Shuang-Xi Gu . A chiral fluorescent probe for molecular recognition of basic amino acids in solutions and cells. Chinese Chemical Letters, 2024, 35(10): 109862-. doi: 10.1016/j.cclet.2024.109862
15. [15]
  Zhenyang Lin . A classification scheme for inorganic cluster compounds based on their electronic structures and bonding characteristics. Chinese Journal of Structural Chemistry, 2024, 43(5): 100254-100254. doi: 10.1016/j.cjsc.2024.100254
16. [16]
  Wen-Tao Ouyang , Jun Jiang , Yan-Fang Jiang , Ting Li , Yuan-Yuan Liu , Hong-Tao Ji , Li-Juan Ou , Wei-Min He . Sono-photocatalytic amination of quinoxalin-2(1H)-ones with aliphatic amines. Chinese Chemical Letters, 2024, 35(10): 110038-. doi: 10.1016/j.cclet.2024.110038
17. [17]
  Yue Li , Minghao Fan , Conghui Wang , Yanxun Li , Xiang Yu , Jun Ding , Lei Yan , Lele Qiu , Yongcai Zhang , Longlu Wang . 3D layer-by-layer amorphous MoS_x assembled from [Mo₃S₁₃]^2- clusters for efficient removal of tetracycline: Synergy of adsorption and photo-assisted PMS activation. Chinese Chemical Letters, 2024, 35(9): 109764-. doi: 10.1016/j.cclet.2024.109764
18. [18]
  Xing Tian , Di Wu , Wanheng Wei , Guifu Dai , Zhanxian Li , Benhua Wang , Mingming Yu . A lipid droplets-targetable fluorescent probe for polarity detection in cells of iron death, inflammation and fatty liver tissue. Chinese Chemical Letters, 2024, 35(6): 108912-. doi: 10.1016/j.cclet.2023.108912
19. [19]
  Linfang Wang , Jing Liu , Minghao Ren , Wei Guo . A highly sensitive fluorescent HClO probe for discrimination between cancerous and normal cells/tissues. Chinese Chemical Letters, 2024, 35(6): 108945-. doi: 10.1016/j.cclet.2023.108945
20. [20]
  Liangji Chen , Zhen Yuan , Fudong Feng , Xin Zhou , Zhile Xiong , Wuji Wei , Hao Zhang , Banglin Chen , Shengchang Xiang , Zhangjing Zhang . A hydrogen-bonded organic framework containing fluorescent carbazole and responsive pyridyl units for sensing organic acids. Chinese Chemical Letters, 2024, 35(9): 109344-. doi: 10.1016/j.cclet.2023.109344

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(179)
HTML views(3)

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