Citation: Ling-Yun XIN, Xiao-Ling LI, Wei-Dong YIN, Guang-Zhen LIU. Two Carboxylato-bridged Binuclear Cobalt(Ⅱ) Complexes Pillared Coligands: Synthesis, Structures and Magnetic Properties[J]. Chinese Journal of Structural Chemistry, ;2020, 39(5): 933-941. doi: 10.14102/j.cnki.0254-5861.2011-2503 shu

Two Carboxylato-bridged Binuclear Cobalt(Ⅱ) Complexes Pillared Coligands: Synthesis, Structures and Magnetic Properties

a.
College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-oriented Porous Materials, Luoyang Normal University, Luoyang, Henan 471934, China
b.
School of Food and Drug, Luoyang Normal University, Luoyang, Henan 471934, China

Corresponding author: Guang-Zhen LIU, gzliuly@126.com
Received Date: 20 June 2019
Accepted Date: 12 October 2019

Fund Project: the National Natural Science Foundation of China 21571093Colleges and Universities Key Scientific Research Project of Henan Province 18B150016

Figures(6)

By adopting mixed-ligand strategy, two Co(Ⅱ) coordination polymers, [Co(phda)(itmb)(H₂O)₂]_n (1) and [Co(phda)(Hpytz)]_n (2) (H₂phda = 1, 2-phenylenediacetate, itmb = 1-(imidazo-1-ly)-4-(1, 2, 4-triazol-1-yl methyl) benzene and Hpytz = 3, 5-di(4-pyridyl)-1, 2, 4-triazolate), were hydrothermally synthesized and then characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The single-crystal X-ray diffraction reveals that two complexes feature carboxylato-bridged binuclear subunits extended further by the nitrogen-rich coligands to form different structures. Complex 1 containing phda-bridged binuclear cobalt is developed by itmb coligand to 1D double-stranded chain, whereas complex 2 exhibits 2D open bilayers, which result from the ribbon-like carboxylate chains pillared Hpytz coligands. In addition, the magnetic susceptibilities of both compounds were measured over the temperature range of 3~300 K, and the data were analyzed well using MagSaki software. The best fitting parameters were κ = 0.98, λ = −100 cm^-1, ∆ = 588 cm^-1 and J = 0.6 cm^-1 for complex 1 and κ = 0.86, λ = −110 cm^-1, ∆ = 756.8 cm^-1 and J = −1.25 cm^-1 for complex 2. The results indicate the existence of weaker ferromagnetic interaction for complex 1 and antiferromagnetic interaction for complex 2 between the metal centers in the dinuclear metal units.
- mixed-ligand,
- complexes,
- synthesis,
- structures,
- magnetic properties
1. [1]
  Kurmoo, M. Magnetic metal-organic frameworks. Chem. Soc. Rev. 2009, 38, 1353–1379. doi: 10.1039/b804757j
2. [2]
  Nandi, S.; Collins, S.; Chakraborty, D.; Banerjee, D.; Thallapally, P. K.; Woo, T. K.; Vaidhyanathan, R. Ultralow parasitic energy for postcombustion CO₂ capture realized in a nickel isonicotinate metal-organic framework with excellent moisture stability. J. Am. Chem. Soc. 2017, 139, 1734–1737. doi: 10.1021/jacs.6b10455
3. [3]
  Liu, J. Q.; Wang, W. J.; Luo, Z. D.; Li, B. H.; Yuan, D. Q. Microporous metal-organic framework based on ligand-truncation strategy with high performance for gas adsorption and separation. Inorg. Chem. 2017, 56, 10215–10219. doi: 10.1021/acs.inorgchem.7b00851
4. [4]
  Lian, X.; Yan, B. Phosphonate MOFs composite as off-on fluorescent sensor for detecting purine metabolite uric acid and diagnosing hyperuricuria. Inorg. Chem. 2017, 56, 6802–6808. doi: 10.1021/acs.inorgchem.6b03009
5. [5]
  Zhao, Y.; Deng, D. S.; Ma, L. F.; Ji, B. M.; Wang, L. Y. A new copper-based metal-organic framework as a promising heterogeneous catalyst for chemo-and regio-selective enamination of b-ketoesters. Chem. Commun. 2013, 49, 10299–10301. doi: 10.1039/c3cc45310c
6. [6]
  Rocca, J. D.; Liu, D. M.; Lin, W. B. Nanoscale metal-organic frameworks for biomedical imaging and drug delivery. Acc. Chem. Res. 2011, 44, 957–968. doi: 10.1021/ar200028a
7. [7]
  Liu, S. J.; Han, S. D.; Zhao, J. P.; Xu, J.; Bu, X. H. In-situ synthesis of molecular magnetorefrigerant materials. Coord. Chem. Rev. 2019, 394, 39–52. doi: 10.1016/j.ccr.2019.05.009
8. [8]
  Maruyama, T.; Kikukawa, Y.; Sakiyama, H.; Katayama, M.; Inada, Y.; Hayashi, Y. A highly-flexible cyclic-decavanadate ligand for interconversion of dinuclear-and trinuclear cobalt(Ⅱ) and manganese(Ⅱ) cores. RSC Adv. 2017, 7, 37666–37674. doi: 10.1039/C7RA05941H
9. [9]
  Gadzikwa, T.; Farha, O. K.; Malliakas, C. D.; Kanatzidis, M. G.; Hupp, J. T.; Nguyen, S. T. Selective bifunctional modification of a non-catenated metal-organic framework material via "click" chemistry. J. Am. Chem. Soc. 2009, 131, 13613–13615. doi: 10.1021/ja904189d
10. [10]
  Zhuang, W. J.; Sun, H. L.; Xu, H. B.; Wang, Z. M.; Gao, S.; Jin, L. P. Reversible de-/resolvation and accompanied magnetism modulation in a framework of topologically ferrimagnetic [Co₃(μ³-OH)₂]_n chains linked by a V-shaped ligand 4, 4΄-dicarboxybiphenyl sulfone. Chem. Commun. 2010, 46, 4339–4341. doi: 10.1039/c002426k
11. [11]
  Cheng, J. W.; Zheng, S. T.; Yang, G. Y. Diversity of crystal structure with different lanthanide ions involving in situ oxidation-hydrolysis reaction. Dalton Trans. 2007, 4059–4066.
12. [12]
  Liu, G. Z.; Li, S. H.; Wang, L. Y. Five M(Ⅱ) coordination polymers assembled from various polynuclear units spaced by semirigid carboxyphenylpropionate and N-donor coligand. CrystEngComm. 2012, 14, 880–889. doi: 10.1039/C1CE05926B
13. [13]
  Xin, L. Y.; Liu, G. Z.; Ma, L. F.; Li, G. L.; Wang, L. Y. Guest water-controlled reversible crystalline-to-amorphous transition and concomitant fluorescence shift in a polar open coordination polymer. Inorg. Chim. Acta 2016, 443, 64–68. doi: 10.1016/j.ica.2015.12.022
14. [14]
  Liu, T. F.; Lü, J.; Cao, R. Coordination polymers based on flexible ditopic carboxylate or nitrogen-donor ligands. CrystEngComm. 2010, 12, 660–670. doi: 10.1039/B914145F
15. [15]
  Liu, G. Z.; Li, X. D.; Xin, L. Y.; Li, X. L.; Wang, L. Y. J. Diverse assemblies of the (4, 4) grid layers exemplified in Zn(Ⅱ)/Co(Ⅱ) coordination polymers with dual linear ligands. J. Solid State Chem. 2013, 203, 106–113. doi: 10.1016/j.jssc.2013.03.053
16. [16]
  Ju, F. Y.; Li, Y. P.; Li, G. L.; Liu, G. Z.; Xin, L. Y.; Li, X. L. Zinc(Ⅱ) and cadmium(Ⅱ) coordination polymers with various polynuclears spaced by semirigid 4-carboxybenzeneacetate and nitrogen-rich co-ligands: syntheses, structures and properties. Chin. J. Inorg. Chem. 2016, 32, 1876–1884.
17. [17]
  Huang, K. L.; Liu, X.; Li, J. K. Three-dimensional metal(Ⅱ)-organic coordination polymers from binuclear, trinuclear and polynuclear clusters bridged by p-benzenediacrylates: syntheses, topologies, photosensitive properties and hydrogen uptake. Cryst. Growth Des. 2010, 10, 1508–1515. doi: 10.1021/cg900579s
18. [18]
  Ju, F. Y.; Li, Y. P.; Li, G. L.; Liu, G. Z. Syntheses, crystal structures, and magnetic properties of cobalt(Ⅱ) cmplexes with 1, 1-cyclohexanediacetic acid. Chin. J. Struct. Chem. 2016, 35, 404–412.
19. [19]
  Xin, L. Y.; Liu, G. Z.; Ma, L. F.; Zhang, X.; Wang, L. Y. Structural diversity and fluorescence regulation of three Zn^Ⅱ coordination polymers assembled from mixed ligands tectons. Aust. J. Chem. 2015, 68, 758–765. doi: 10.1071/CH14347
20. [20]
  Xin, L. Y.; Liu, G. Z.; Wang, L. Y. New coordination polymers from 1D chain, 2D layer to 3D framework constructed from 1, 2-phenylene diacetic acid and 1, 3-bis(4-pyridyl)propane flexible ligands. J. Solid State Chem. 2011, 184, 1387–1392. doi: 10.1016/j.jssc.2011.04.002
21. [21]
  Xin, L. Y.; Liu, G. Z.; Li, X. L.; Wang, L. Y. Structural diversity for a series of metal(Ⅱ) complexes based on flexible 1, 2-phenylenediacetate and dipyridyl-type coligand. Cryst. Growth Des. 2012, 12, 147–157. doi: 10.1021/cg200903k
22. [22]
  Kang, W. C.; Li, Y. H.; Qin, Z. B.; Cui, G. H. Synthesis, structures and characterization of two cobalt(Ⅱ) coordination polymers with 2, 5‑dichloroterephthalic acid and fexible bis(benzimidazole) ligands. Transit. Metal Chem. 2018, 43, 563–570. doi: 10.1007/s11243-018-0242-4
23. [23]
  Kang, H. X.; Fu, Y. Q.; Xin, L. Y.; Li, G. L.; Ma, L. F.; Liu, G. Z. Two coordination polymers containing linear Co(Ⅱ)-trinuclear and Cu(Ⅱ)-chain assembled from 4-fluorocinnamic acid and N-donor ligand. Chin. J. Struct. Chem. 2016, 35, 286–292.
24. [24]
  Pasán, J.; Sanchiz, J.; Fabelo, Ó.; Delgado, L. C.; Déniz, M.; Gallifa, P. D.; Benito, C. M.; Lloret, F.; Julve, M.; Pérez, C. R. Influence of the coligand in the magnetic properties of a series of copper(Ⅱ)-phenylmalonate complexes. CrystEngComm. 2014, 16, 8106–8118. doi: 10.1039/C4CE00834K
25. [25]
  Xin, L. Y.; Ju, F. Y.; Li, X. L.; Liu, G. Z. Thermal stabilities and crystal structures of two supramolecular microporous frameworks based on carboxylate-dipyridyl mix-ligands. Russ. J. Coord. Chem. 2017, 43, 55–62. doi: 10.1134/S1070328417010080
26. [26]
  Liu, G. Z.; Li, S. H.; Li, X. L.; Xin, L. Y.; Wang, L. Y. Three series of MOFs featuring various metal(Ⅱ)-carboxylate chains cross-linked by dipyridyl-typed coligands: synthesis, structure, and solvent-dependent luminescence. CrystEngComm. 2013, 15, 4571–4580. doi: 10.1039/c3ce40109j
27. [27]
  Li, X. L.; Liu, G. Z.; Xin, L. Y.; Wang, L. Y. Binuclear and tetranuclear Mn(Ⅱ) clusters in coordination polymers derived from semirigid tetracarboxylate and N‑donor ligands: syntheses, new topology structures and magnetism. J. Solid State Chem. 2017, 246, 252–257. doi: 10.1016/j.jssc.2016.11.030
28. [28]
  Liu, G. C.; Yu, H. X.; Lin, H. Y.; Wang, X. L.; Li, X. W. Spacers-induced structural diversity of cobalt coordination polymers based on "V"-type dipyridylamide and dicarboxylic ligands: fluorescent, magnetic and photocatalytic properties. Polyhedron 2017, 126, 205–213. doi: 10.1016/j.poly.2017.01.022
29. [29]
  Chen, Z. W.; Mi, X. N.; Lu, J.; Wang, S. N.; Li, Y. W.; Dou, J. M.; Li, D. C. From 2D-3D interpenetration to packing: N coligand-driven structural assembly and tuning of luminescent sensing activities towards Fe³⁺ and Cr₂O₇²⁻ ions. Dalton Trans. 2018, 47, 6240–6249. doi: 10.1039/C8DT00909K
30. [30]
  Sakiyama, H. Development of MagSaki software for magnetic analysis of dinuclear high-spin cobalt(Ⅱ) complexes in an axially distorted octahedral field. J. Chem. Soft. 2001, 7, 171–178. doi: 10.2477/jchemsoft.7.171
31. [31]
  Sheldrick, G. M. A Program for the Siemens Area Detector Absorption Correction. University of Göttingen, Germany 1997.
32. [32]
  Spek, A. L. PLATON, A Multi-purpose Crystallographic Tool. Utrecht (Netherlands): Utrecht University 2001.
33. [33]
  Sheldrick, G. M. SHELXS-97, Program for the Solution of Crystal Structures. University of Gottingen, Göttingen, Germany 1997.
34. [34]
  Sheldrick, G. M. SHELXL-97, Program for Refinement of Crystal Structures. University of Gottingen, Göttingen, Germany 1997.
35. [35]
  Huang, F. P.; Tian, J. L.; Gu, W.; Liu, X.; Yan, S. P.; Liao, D. Z.; Cheng, P. Co(Ⅱ) coordination polymers: positional isomeric effect, structural and magnetic diversification. Cryst. Growth Des. 2010, 10, 1145–1154. doi: 10.1021/cg901014r
36. [36]
  Sakiyama, H.; Ito, R.; Kumagai, H.; Inoue, K.; Sakamoto, M.; Nishida, Y.; Yamasaki, M. Dinuclear cobalt(Ⅱ) complexes of an acyclic phenol-based dinucleating ligand with four methoxyethyl chelating arms first magnetic analyses in an axially distorted octahedral field. Eur. J. Inorg. Chem. 2001, 2027–2032.
37. [37]
  Hossain, M. J.; Yamasaki, M.; Mikuriya, M.; Kuribayashi, A.; Sakiyama, H. Synthesis, structure, and magnetic properties of dinuclear cobalt(Ⅱ) complexes with a new phenol-based dinucleating ligand with four hydroxyethyl chelating arms. Inorg. Chem. 2002, 41, 4058–4062. doi: 10.1021/ic0255297
38. [38]
  Sakamoto, M.; Nishida, Y.; Yamasaki, M. Dinuclear cobalt(Ⅱ) complexes of an acyclic phenol-based dinucleating ligand with four methoxyethyl chelating arms first magnetic analyses in an axially distorted octahedral field. Eur. J. Inorg. Chem. 2001, 2705.
39. [39]
  Wang, L.; Gu, W.; Deng, J. X.; Liu, M. L.; Xu, N.; Liu, X. Syntheses, structures, and photoluminescent and magnetic properties of four novel complexes constructed from 2, 4, 5-tri(4-pyridyl)-imidazole and benzene-1, 3, 5-tricarboxylic acid. Z. Anorg. Allg. Chem. 2010, 636, 1124–1128. doi: 10.1002/zaac.200900436
40. [40]
  Li, X. J.; Guan, T. N.; Guo, X. F.; Li, X. X.; Yu, Z. J. Construction of metal-organic frameworks consisting of dinuclear metal units based on 5-hydroxyisophthalate and flexible dipyridyl ligands. Eur. J. Inorg. Chem. 2014, 2307–2316.
1. [1]
  Anqiu LIU , Long LIN , Dezhi ZHANG , Junyu LEI , Kefeng WANG , Wei ZHANG , Junpeng ZHUANG , Haijun HAO . Synthesis, structures, and catalytic activity of aluminum and zinc complexes chelated by 2-((2,6-dimethylphenyl)amino)ethanolate. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 791-798. doi: 10.11862/CJIC.20230424
2. [2]
  Chao LIU , Jiang WU , Zhaolei JIN . Synthesis, crystal structures, and antibacterial activities of two zinc(Ⅱ) complexes bearing 5-phenyl-1H-pyrazole group. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1986-1994. doi: 10.11862/CJIC.20240153
3. [3]
  Jimin HOU , Mengyang LI , Chunhua GONG , Shaozhuang ZHANG , Caihong ZHAN , Hao XU , Jingli XIE . Synthesis, structures, and properties of metal-organic frameworks based on bipyridyl ligands and isophthalic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 549-560. doi: 10.11862/CJIC.20240348
4. [4]
  Xiaofen GUAN , Yating LIU , Jia LI , Yiwen HU , Haiyuan DING , Yuanjing SHI , Zhiqiang WANG , Wenmin WANG . Synthesis, crystal structure, and DNA-binding of binuclear lanthanide complexes based on a multidentate Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2486-2496. doi: 10.11862/CJIC.20240122
5. [5]
  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
6. [6]
  Chaochao Jin , Kai Li , Jiongpei Zhang , Zhihua Wang , Jiajing Tan . N,O-Bidentated difluoroboron complexes based on pyridine-ester enolates: Facile synthesis, post-complexation modification, optical properties, and applications. Chinese Chemical Letters, 2024, 35(9): 109532-. doi: 10.1016/j.cclet.2024.109532
7. [7]
  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
8. [8]
  Zhiwen HUANG , Qi LIU , Jianping LANG . W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 79-87. doi: 10.11862/CJIC.20240184
9. [9]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
10. [10]
  Jing WU , Puzhen HUI , Huilin ZHENG , Pingchuan YUAN , Chunfei WANG , Hui WANG , Xiaoxia GU . Synthesis, crystal structures, and antitumor activities of transition metal complexes incorporating a naphthol-aldehyde Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2422-2428. doi: 10.11862/CJIC.20240278
11. [11]
  Luyao Lu , Chen Zhu , Fei Li , Pu Wang , Xi Kang , Yong Pei , Manzhou Zhu . Ligand effects on geometric structures and catalytic activities of atomically precise copper nanoclusters. Chinese Journal of Structural Chemistry, 2024, 43(10): 100411-100411. doi: 10.1016/j.cjsc.2024.100411
12. [12]
  Jiaqi Ma , Lan Li , Yiming Zhang , Jinjie Qian , Xusheng Wang . Covalent organic frameworks: Synthesis, structures, characterizations and progress of photocatalytic reduction of CO2. Chinese Journal of Structural Chemistry, 2024, 43(12): 100466-100466. doi: 10.1016/j.cjsc.2024.100466
13. [13]
  Min-Hang Zhou , Jun Jiang , Wei-Min He . EDA-complexes-enabled photochemical synthesis of α-amino acids with imines and tetrabutylammonium oxalate. Chinese Chemical Letters, 2025, 36(1): 110446-. doi: 10.1016/j.cclet.2024.110446
14. [14]
  Yao HUANG , Yingshu WU , Zhichun BAO , Yue HUANG , Shangfeng TANG , Ruixue LIU , Yancheng LIU , Hong LIANG . Copper complexes of anthrahydrazone bearing pyridyl side chain: Synthesis, crystal structure, anticancer activity, and DNA binding. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 213-224. doi: 10.11862/CJIC.20240359
15. [15]
  Shuwen SUN , Gaofeng WANG . Two cadmium coordination polymers constructed by varying Ⅴ-shaped co-ligands: Syntheses, structures, and fluorescence properties. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 613-620. doi: 10.11862/CJIC.20230368
16. [16]
  Huirong LIU , Hao XU , Dunru ZHU , Junyong ZHANG , Chunhua GONG , Jingli XIE . Syntheses, structures, photochromic and photocatalytic properties of two viologen-polyoxometalate hybrid materials. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1368-1376. doi: 10.11862/CJIC.20240066
17. [17]
  Xiaoyu Chen , Jiahao Hu , Jingyi Lin , Haiyang Huang , Changqing Ye , Hongli Bao . Biisoindolylidene solvatochromic fluorophores: Synthesis and photophysical properties. Chinese Chemical Letters, 2025, 36(2): 109923-. doi: 10.1016/j.cclet.2024.109923
18. [18]
  Jing LIANG , Qian WANG , Junfeng BAI . Synthesis and structures of cdq-topological quaternary and (4, 4, 8)-c topological quinary Zn-MOFs with both oxalic acid and triazole ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2186-2192. doi: 10.11862/CJIC.20240177
19. [19]
  Tao Yu , Vadim A. Soloshonok , Zhekai Xiao , Hong Liu , Jiang Wang . Probing the dynamic thermodynamic resolution and biological activity of Cu(Ⅱ) and Pd(Ⅱ) complexes with Schiff base ligand derived from proline. Chinese Chemical Letters, 2024, 35(4): 108901-. doi: 10.1016/j.cclet.2023.108901
20. [20]
  Jumei Zhang , Ziheng Zhang , Gang Li , Hongjin Qiao , Hua Xie , Ling Jiang . Ligand-mediated reactivity in CO oxidation of yttrium-nickel monoxide carbonyl complexes. Chinese Chemical Letters, 2025, 36(2): 110278-. doi: 10.1016/j.cclet.2024.110278

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(301)
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