Citation: Ming WANG, Xiao-Mei WANG, Ming-Yu CHEN, Cheng LIU, Ge DING, Xin-Hui ZHOU. A Water-stable Tetranuclear Cd(Ⅱ) Bicyclic Complex Used for the Picric Acid Detection[J]. Chinese Journal of Structural Chemistry, ;2021, 40(11): 1461-1468. doi: 10.14102/j.cnki.0254–5861.2011–3182 shu

A Water-stable Tetranuclear Cd(Ⅱ) Bicyclic Complex Used for the Picric Acid Detection

Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing 210023, China

Corresponding author: Xin-Hui ZHOU, iamxhzhou@njupt.edu.cn
Received Date: 18 March 2021
Accepted Date: 8 June 2021

Fund Project: the National Natural Science Foundation of China 21973047Jiangsu Province Double Innovation Talent Program 090300014001

Figures(7)

By solvothermal reaction of Cd(Ⅱ) with organic ligand N, N΄-bis(3, 5-dicarboxylphenyl)-thiophene-2, 5-dicarboxamide (H₄L), a water-stable complex [Cd₄(H₂L)₄(H₂O)₁₀]·2CH₃OH·8H₂O·4DMF (1, C₁₀₂H₁₂₀Cd₄N₁₂O₆₄S₄) has been successfully synthetized (DMF = N, N-dimethylformamide). 1 crystallizes in the triclinic space group of P\begin{document}$ \overline 1 $\end{document} with a = 11.815(7), b = 16.209(9), c = 16.742(9) Å, α = 82.224(13)º, β = 76.741(13)º, γ = 70.313(12)º, V = 2932(3) Å³, M_r = 3115.93, Z = 1, F(000) = 1584, D_c = 1.765 Mg/cm³, µ = 0.901 mm⁻¹, GOOF = 1.101, the final R = 0.0391 and wR = 0.1297 for 9007 observed reflections (I > 2σ(I)). 1 is a tetranuclear Cd(Ⅱ) bicyclic complex with strong ligand-based blue emission and can stably exist in aqueous solutions over the pH range of 2-11. 1 exhibits high sensitivity, selectivity and anti-interference capability for picric acid (PA) detection in aqueous solution by luminescent quenching. The value of quenching constant (K_sv) is 3.2 × 10⁴ M^-1 within the PA concentration range of 0~40 μM and the detection limit is 6.89 × 10^-7 M. Lastly, we went into depth on possible mechanism of the luminescent quenching.
- sensors,
- complex,
- picric acid,
- fluorescence
1. [1]
  Xu, T. Y.; Li, J. M.; Han, Y. H.; Wang, A. R.; He, K. H.; Shi, Z. F. A new 3D four-fold interpenetrated dia-like luminescent Zn(Ⅱ)-based metal-organic framework: the sensitive detection of Fe³⁺, Cr₂O₇²⁻, and CrO₄²⁻ in water, and nitrobenzene in ethanol. New J. Chem. 2020, 44, 4011–4022. doi: 10.1039/C9NJ06056A
2. [2]
  Zhuang, X. R.; Zhang, X.; Zhang, N. X.; Wang, Y.; Zhao, L. Y.; Yang, Q. F. Novel multifunctional Zn metal-organic framework fluorescent probe demonstrating unique sensitivity and selectivity for detection of PA and Fe³⁺ ions in water solution. Cryst. Growth Des. 2019, 19, 5729–5736. doi: 10.1021/acs.cgd.9b00704
3. [3]
  Jiang, W.; Yang, J. Q.; Yan, G. S.; Zhou, S.; Liu, B.; Qiao, Y.; Zhou, T. Y.; Wang, J. J.; Che, G. B. A novel 3-fold interpenetrated dia metal-organic framework as a heterogeneous catalyst for CO₂ cycloaddition. Inorg. Chem. Commun. 2020, 3, 113, 10770.
4. [4]
  Ren, S. S.; Jiang, W.; Wang, Q, W.; Li, Z. M.; Qiao, Y.; Che, G. B. Synthesis, structures and properties of six lanthanide complexes based on a 2-(2-carboxyphenyl)imidazo(4, 5-f)-(1, 10)phenanthroline ligand. RSC Adv. 2019, 9, 3102–3112. doi: 10.1039/C8RA09207A
5. [5]
  Zhu, J. Y.; Xia, T. F.; Cui, Y. J.; Yang, Y.; Qian, G. D. A turn-on MOF-based luminescent sensor for highly selective detection of glutathione. J. Solid State Chem. 2019, 270, 317–323. doi: 10.1016/j.jssc.2018.11.032
6. [6]
  Fan, K.; Bao, S. S.; Nie, W. X.; Liao, C. H.; Zheng, L. M. Iridium(Ⅲ)-based metal-organic frameworks as multiresponsive luminescent sensors for Fe³⁺, Cr₂O₇^2–, and ATP^2– in aqueous media. Inorg. Chem. 2018, 57, 1079–1089. doi: 10.1021/acs.inorgchem.7b02513
7. [7]
  Luz, I.; Parvathikar, S.; Carpenter, M.; Bellamy, T.; Amato, K. MOF-derived nanostructured catalysts for low-temperature ammonia synthesis. J. Carpenter, M. Lail, Catal. Sci. Technol. 2020, 10, 105–112. doi: 10.1039/C9CY01303B
8. [8]
  Li, Y. Z.; Wang, G. D.; Yang, H. Y.; Hou, L.; Wang, Y. Y.; Zhu, Z. H. Novel cage-like MOF for gas separation, CO₂ conversion and selective adsorption of an organic dye. Inorg. Chem. Front. 2020, 7, 746–755. doi: 10.1039/C9QI01262A
9. [9]
  Guo, H.; Wu, N.; Xue, R.; Liu, H.; Li, L.; Wang, M. Y.; Yao, W. Q.; Li, Q.; Yang, W. Multifunctional Ln-MOF luminescent probe displaying superior capabilities for highly selective sensing of Fe³⁺ and Al³⁺ ions and nitrotoluene. Colloid Surface A 2020, 585, 124094. doi: 10.1016/j.colsurfa.2019.124094
10. [10]
  Moradi, E.; Rahimi, R.; Farahani, Y. D.; Safarifard, V. Porphyrinic zirconium-based MOF with exposed pyrrole Lewis base site as a luminescent sensor for highly selective sensing of Cd²⁺ and Br⁻ ions and THF small molecule. J. Solid State Chem. 2020, 282, 121103. doi: 10.1016/j.jssc.2019.121103
11. [11]
  Igoa, F.; Peinado, G.; Suescun, L.; Kremer, C.; Torres, J. Design of a white-light emitting material based on a mixed-lanthanide metal organic framework. J. Solid State Chem. 2019, 279, 120925. doi: 10.1016/j.jssc.2019.120925
12. [12]
  Zhan, Z. Y.; Liang, X. Y.; Zhang, X. L.; Jia, Y. J.; Hu, M. A water-stable europium-MOF as a multifunctional luminescent sensor for some trivalent metal ions (Fe³⁺, Cr³⁺, Al³⁺), PO₄³⁻ ions, and nitroaromatic explosives. Dalton Trans. 2019, 48, 1786–1794. doi: 10.1039/C8DT04653K
13. [13]
  Xiao, J. N.; Liu, J. J.; Gao, X. C.; Ji, G. F.; Wang, D. B.; Liu, Z. L. A multi-chemosensor based on Zn-MOF: ratio-dependent color transition detection of Hg(Ⅱ) and highly sensitive sensor of Cr (VI). Sensor Actuat. B-Chem. 2018, 269, 164–172. doi: 10.1016/j.snb.2018.04.129
14. [14]
  Xu, H.; Xiao, Y. Q.; Rao, X. T.; Dou, Z. S.; Li, W. F.; Cui, Y. J.; Wang, Z. Y.; Qian, G. D. A metal-organic framework for selectively sensing of PO₄³⁻ anion in aqueous solution. J Alloys Compd. 2011, 509, 2552–2554. doi: 10.1016/j.jallcom.2010.11.087
15. [15]
  Qin, Y. R.; Ge, Y.; Zhang, S. S.; Sun, H.; Jing, Y.; Li, Y. H.; Liu, W. A series of Ln₄^Ⅲ clusters: Dy₄ single molecule magnet and Tb₄ multi-responsive luminescent sensor for Fe³⁺, CrO₄²⁻/Cr₂O₇²⁻ and 4-nitroaniline. RSC Adv. 2018, 8, 12641–12652. doi: 10.1039/C8RA01485J
16. [16]
  Yang, Y.; Chen, L.; Jiang, F. L; Wu, M. Y.; Pang, J. D.; Wan, X. Y.; Hong, M. C. A water-stable 3D Eu-MOF based on a metallacyclodimeric secondary building unit for sensitive fluorescent detection of acetone molecules. CrystEngComm. 2019, 21, 321–328. doi: 10.1039/C8CE01875H
17. [17]
  Cui, Y.; Chen, F.; Yin, X. B. A ratiometric fluorescence platform based on boric-acid-functional Eu-MOF for sensitive detection of H₂O₂ and glucose. Biosens Bioelection 2019, 135, 208–215. doi: 10.1016/j.bios.2019.04.008
18. [18]
  Yu, L.; Zheng, Q. T.; Wu, D.; Xiao, Y. X. Bimetal-organic framework nanocomposite based point-of-care visual ratiometric fluorescence pH microsensor for strong acidity. Sensor Actuat. B-Chem. 2019, 294, 199–205. doi: 10.1016/j.snb.2019.05.037
19. [19]
  Liu, W.; Wang, Y. L.; Song, L. P.; Silver, M. A.; Xie, J.; Zhang, L. M.; Chen, L. H.; Diwu, J.; Chai, Z. F.; Wang, S. Efficient and selective sensing of Cu²⁺ and UO₂²⁺ by a europium metal-organic framework. Talanta. 2019, 196, 515–522. doi: 10.1016/j.talanta.2018.12.088
20. [20]
  Zhou, X. H.; Chen, Q. Q.; Liu, B. L.; Li, L.; Yang, T.; Huang, W. Syntheses, structures and magnetic properties of nine coordination polymers based on terphenyl-tetracarboxylic acid ligands. Dalton Trans. 2017, 46, 430–444. doi: 10.1039/C6DT04270H
21. [21]
  Fu, H. R.; Wu, X. X.; Ma, L. F.; Wang, F.; Zhang, J. Dual-emission SG7@MOF sensor via SC–SC transformation: enhancing the formation of excimer emission and the range and sensitivity of detection. ACS Appl. Mater. Interfaces 2018, 10, 18012–18020. doi: 10.1021/acsami.8b05614
22. [22]
  Luo, J.; Liu, B. S.; Zhang, X. R.; Liu, R. T. A Eu³⁺ post-functionalized metal-organic framework as fluorescent probe for highly selective sensing of Cu²⁺ in aqueous media. J. Mol. Stuct. 2019, 1177, 444–448. doi: 10.1016/j.molstruc.2018.09.091
23. [23]
  Wu, K. Y.; Qin, L.; Fan, C.; Cai, S. L.; Zhang, T. T.; Chen, W. H.; Tang, X. Y.; Chen, J. X. Sequential and recyclable sensing of Fe³⁺ and ascorbic acid in water with a terbium(Ⅲ)-based metal-organic framework. Dalton Trans. 2019, 48, 8911–8919. doi: 10.1039/C9DT00871C
24. [24]
  Feng, X.; Guo, N.; Li, R. F.; Chen, H. P.; Ma, L. F.; Li, Z. J.; Wang, L. Y. A facile route for tuning emission and magnetic properties by controlling lanthanide ions in coordination polymers incorporating mixed aromatic carboxylate ligands. J. Solid State Chem. 2018, 268, 22–29. doi: 10.1016/j.jssc.2018.08.017
25. [25]
  Li, R.; Qu, X. L.; Zhang, Y. H.; Han, H. L.; Li, X. Lanthanide-organic frameworks constructed from naphthalenedisulfonates: structure, luminescence and luminescence sensing properties. CrystEngComm. 2016, 18, 5890–5900. doi: 10.1039/C6CE01028H
26. [26]
  Cao, A. P.; Zhu, W.; Shang, J.; Klootwijk, J. H.; Sudhölter, E. J. R.; Huskens, J.; de Smet, L. C. P. M. Metal-organic polyhedra-coated Si nanowires for the sensitive detection of trace explosives. Nano Lett. 2017, 17, 1-7. doi: 10.1021/acs.nanolett.6b02360
27. [27]
  Wu, X. X.; Fu, H. R.; Han, M. L.; Zhou, Z.; Ma, L. F. Tetraphenylethylene immobilized metal-organic frameworks: highly sensitive fluorescent sensor for the detection of Cr₂O₇^2– and nitroaromatic explosives. Cryst. Growth Des. 2017, 17, 6041–6084. doi: 10.1021/acs.cgd.7b01155
28. [28]
  Hu, Y. L.; Ding, M. L.; Liu, X. Q.; Sun, L. B.; Jiang, H. L. Rational synthesis of an exceptionally stable Zn(Ⅱ) metal-organic framework for the highly selective and sensitive detection of picric acid. Chem. Commun. 2016, 52, 5734–5737. doi: 10.1039/C6CC01597B
29. [29]
  Liang, Y. T.; Yang, G. P.; Liu, B.; Yan, Y. T.; Xia, Z. P.; Wang, Y. Y. Four super water-stable lanthanide-organic frameworks with active uncoordinated carboxylic and pyridyl groups for selective luminescence sensing of Fe³⁺. Dalton Trans. 2015, 44, 13325–13330. doi: 10.1039/C5DT01421B
30. [30]
  Wang, G. Y.; Song, C.; Kong, D. M.; Ruan, W. J.; Chang, Z.; Li, Y. Two luminescent metal-organic frameworks for the sensing of nitroaromatic explosives and DNA strands. J. Mater. Chem. A 2014, 2, 2213–2220. doi: 10.1039/C3TA14199C
31. [31]
  Sheldrick, G. M. SHELXS-2014, Program for Crystal Structure Solution. University of Gottingen, Germany 2014.
32. [32]
  Sheldrick, G. M. SHELXL-2014, Program for the Refinement of Crystal Structure. University of Gottingen, Germany 2014.
33. [33]
  Sheldrick, G. M. SADABS, Program for Empirical Absorption Correction of Area Detector Data. University of Gottingen, Gottingen Germany 1997.
34. [34]
  Chen, D. M.; Zhang, N. N.; Liu, C. S.; Du, M. Dual-emitting dye@MOF composite as a self-calibrating sensor for 2, 4, 6-trinitrophenol. ACS Appl. Mater. Interfaces 2017, 9, 24671–24677. doi: 10.1021/acsami.7b07901
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]
  Lulu DONG , Jie LIU , Hua YANG , Yupei FU , Hongli LIU , Xiaoli CHEN , Huali CUI , Lin LIU , Jijiang WANG . Synthesis, crystal structure, and fluorescence properties of Cd-based complex with pcu topology. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 809-820. doi: 10.11862/CJIC.20240171
3. [3]
  Dongdong YANG , Jianhua XUE , Yuanyu YANG , Meixia WU , Yujia BAI , Zongxuan WANG , Qi MA . Design and synthesis of two coordination polymers for the rapid detection of ciprofloxacin based on triphenylpolycarboxylic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2466-2474. doi: 10.11862/CJIC.20240266
4. [4]
  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
5. [5]
  Yingying Yan , Wanhe Jia , Rui Cai , Chun Liu . An AIPE-active fluorinated cationic Pt(Ⅱ) complex for efficient detection of picric acid in aqueous media. Chinese Chemical Letters, 2024, 35(5): 108819-. doi: 10.1016/j.cclet.2023.108819
6. [6]
  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
7. [7]
  Xiao SANG , Qi LIU , Jianping LANG . Synthesis, structure, and fluorescence properties of Zn(Ⅱ) coordination polymers containing tetra-alkenylpyridine ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2124-2132. doi: 10.11862/CJIC.20240158
8. [8]
  Lu LIU , Huijie WANG , Haitong WANG , Ying LI . Crystal structure of a two-dimensional Cd(Ⅱ) complex and its fluorescence recognition of p-nitrophenol, tetracycline, 2, 6-dichloro-4-nitroaniline. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1180-1188. doi: 10.11862/CJIC.20230489
9. [9]
  Chen LU , Qinlong HONG , Haixia ZHANG , Jian ZHANG . Syntheses, structures, and properties of copper-iodine cluster-based boron imidazolate framework materials. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 149-154. doi: 10.11862/CJIC.20240407
10. [10]
  Xueling Yu , Lixing Fu , Tong Wang , Zhixin Liu , Na Niu , Ligang Chen . Multivariate chemical analysis: From sensors to sensor arrays. Chinese Chemical Letters, 2024, 35(7): 109167-. doi: 10.1016/j.cclet.2023.109167
11. [11]
  Xiaoyan Peng , Xuanhao Wu , Fan Yang , Yefei Tian , Mingming Zhang , Hongye Yuan . Gas sensors based on metal-organic frameworks: challenges and opportunities. Chinese Journal of Structural Chemistry, 2024, 43(3): 100251-100251. doi: 10.1016/j.cjsc.2024.100251
12. [12]
  Chenghao Liu , Xiaofeng Lin , Jing Liao , Min Yang , Min Jiang , Yue Huang , Zhizhi Du , Lina Chen , Sanjun Fan , Qitong Huang . Carbon dots-based dopamine sensors: Recent advances and challenges. Chinese Chemical Letters, 2024, 35(12): 109598-. doi: 10.1016/j.cclet.2024.109598
13. [13]
  Lin Guo , Rui Xu , Denys Makarov . Printable magnetoresistive sensors: A crucial step toward unconventional magnetoelectronics. Chinese Journal of Structural Chemistry, 2025, 44(2): 100428-100428. doi: 10.1016/j.cjsc.2024.100428
14. [14]
  Mengchen Liu , Yufei Zhang , Yi Xiao , Yang Wei , Meichen Bi , Huaide Jiang , Yan Yu , Shenghong Zhong . High stretchability and toughness of liquid metal reinforced conductive biocompatible hydrogels for flexible strain sensors. Chinese Journal of Structural Chemistry, 2025, 44(3): 100518-100518. doi: 10.1016/j.cjsc.2025.100518
15. [15]
  Chao Ma , Cong Lin , Jian Li . MicroED as a powerful technique for the structure determination of complex porous materials. Chinese Journal of Structural Chemistry, 2024, 43(3): 100209-100209. doi: 10.1016/j.cjsc.2023.100209
16. [16]
  Mengjuan Sun , Muye Zhou , Yifang Xiao , Hailei Tang , Jinhua Chen , Ruitao Zhang , Chunjiayu Li , Qi Ya , Qian Chen , Jiasheng Tu , Qiyue Wang , Chunmeng Sun . Reversibly size-switchable polyion complex micelles for antiangiogenic cancer therapy. Chinese Chemical Letters, 2024, 35(7): 109110-. doi: 10.1016/j.cclet.2023.109110
17. [17]
  Yuanjin Chen , Xianghui Shi , Dajiang Huang , Junnian Wei , Zhenfeng Xi . Synthesis and reactivity of cobalt dinitrogen complex supported by nonsymmetrical pincer ligand. Chinese Chemical Letters, 2024, 35(7): 109292-. doi: 10.1016/j.cclet.2023.109292
18. [18]
  Peng Meng , Qian-Cheng Luo , Aidan Brock , Xiaodong Wang , Mahboobeh Shahbazi , Aaron Micallef , John McMurtrie , Dongchen Qi , Yan-Zhen Zheng , Jingsan Xu . Molar ratio induced crystal transformation from coordination complex to coordination polymers. Chinese Chemical Letters, 2024, 35(4): 108542-. doi: 10.1016/j.cclet.2023.108542
19. [19]
  Jingwen Zhao , Jianpu Tang , Zhen Cui , Limin Liu , Dayong Yang , Chi Yao . A DNA micro-complex containing polyaptamer for exosome separation and wound healing. Chinese Chemical Letters, 2024, 35(9): 109303-. doi: 10.1016/j.cclet.2023.109303
20. [20]
  Ya-Ping Liu , Zhi-Rong Gui , Zhen-Wen Zhang , Sai-Kang Wang , Wei Lang , Yanzhu Liu , Qian-Yong Cao . A phenylphenthiazide anchored Tb(Ⅲ)-cyclen complex for fluorescent turn-on sensing of ClO⁻. Chinese Chemical Letters, 2025, 36(2): 109769-. doi: 10.1016/j.cclet.2024.109769

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(277)
HTML views(1)

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