Citation: JIANG Dongmei, BO Le, ZHU Ting, TAO Junbin, YANG Xiaoping. Construction and NIR Luminescence Properties of Zn-Ln Rectangular Nanoclusters[J]. Acta Physico-Chimica Sinica, ;2018, 34(7): 812-817. doi: 10.3866/PKU.WHXB201801086 shu

Construction and NIR Luminescence Properties of Zn-Ln Rectangular Nanoclusters

College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, Zhejiang Province, P. R. China

Corresponding author: YANG Xiaoping, xpyang@wzu.edu.cn
Received Date: 14 December 2017
Revised Date: 29 December 2017
Accepted Date: 3 January 2018
Available Online: 8 July 2018
Fund Project: the National Natural Science Foundation of China 21771141The project was supported by the National Natural Science Foundation of China (21771141)

Heterometallic d-4f nanoclusters are currently of interest due to their potential use in material science and as probes in biology. Self-assembly by metal-ligand coordination is one of the most efficient processes that organize individual molecular components into nanosized species. However, for lanthanide-based self-assemblies, their stoichiometries and structures are difficult to control during synthesis, because the Ln(Ⅲ) ions often display high and variable coordination numbers. As a result, the structures of lanthanide complexes are commonly influenced by a variety of factors, such as the type of metal ions, the formation of ligands, and the nature of counter anions. In this article, two Zn-Ln nanoclusters [Ln₂Zn₂L₂(OAc)₆] (Ln = Yb (1) and Er (2)) were prepared using a new long Schiff base ligand with a Ph(CH₂)Ph backbone. These nanoclusters show interesting rectangular-like structures. The long Schiff base ligand displays a "stretched" configuration and is bound to the metal ions through its N and phenoxide and methoxy O atoms. As a result, large clusters (0.7 nm × 1.1 nm × 2.2 nm for 1) were formed. In the crystal structures of 1 and 2, each Ln³⁺ ion and its closer Zn²⁺ ion are linked by one OAc^- anion and phenolic oxygen atoms of two long Schiff base ligands, forming a ZnLn unit. Two such ZnLn units are then bridged by two Schiff base ligands to form the nano-rectangular structures. Energy dispersive X-ray spectroscopy (EDX) analyses of the clusters indicate that the molar ratio of Zn : Ln is about 1 : 1, in agreement with their crystal structures. Thermogravimetric analyses show that the clusters lose about 5% of the weight when heated to below 100 ℃. Melting point measurements show that the clusters are thermodynamically stable. Upon excitation of the ligand-centered absorption bands, 1 and 2 exhibit the NIR luminescence of Yb³⁺ and Er³⁺, respectively. The clusters show two excitation bands from 250 to 500 nm, in agreement with their absorption spectra, confirming that energy transfer occurs from the Zn/L centers to Ln³⁺ ions. These results indicate that the chromogenic Zn/L components in these nanoclusters can act as efficient sensitizers for lanthanide luminescence. The efficiencies of the energy transfer from Zn/L-centers to Yb³⁺ is higher than that to Er³⁺, being 75.71% and 25.00% for 1 and 2, respectively. These results provide new insights into the design of polynuclear nanoclusters with interesting luminescence properties.
- Construction,
- Zn-Ln nanocluster,
- Schiff base ligand,
- Structure,
- Luminescence
1. [1]
  Li, M.; Tian, S.; Wu, Z.; Jin, R. Chem. Commun.2015, 4433. doi: 10.1039/c4cc08830a doi: 10.1039/c4cc08830a
2. [2]
  Yu, W. L.; Zuo, H. W.; Lu, C. H.; Li, Y.; Zhang, Y. F.; Chen, W. K. Acta Phys. -Chim. Sin. 2015, 31, 425. doi: 10.3866/PKU.WHXB201501191
3. [3]
  Kauffman, D. R.; Alfonso, D.; Matranga, C.; Ohodnicki, P.; Deng, X.; Siva, R. C.; Zeng, C.; Jin, R. Chem. Sci. 2014, 5, 3151. doi: 10.1039/c4sc00997e doi: 10.1039/c4sc00997e
4. [4]
  Qian, H.; Barry, E.; Zhu, Y.; Jin, R. Acta Phys. -Chim. Sin. 2011, 27, 513. doi: 10.3866/PKU.WHXB20110304 doi: 10.3866/PKU.WHXB20110304
5. [5]
  Yang, J. L. Acta Phys. -Chim. Sin. 2017, 33, 1273. doi: 10.3866/PKU.WHXB201704262
6. [6]
  Peng, J. B.; Zhang, Q. C.; Kong, X. J.; Zheng, Y. Z.; Ren, Y. P.; Long, L. S.; Huang, R. B.; Zheng L. S.; Zheng, Z. J. Am. Chem. Soc. 2012, 134, 3314. doi: 10.1021/ja209752z doi: 10.1021/ja209752z
7. [7]
  Wang, B.; Zang, Z.; Wang, H.; Dou, W.; Tang, X.; Liu, W.; Shao, Y.; Ma, J.; Li, Y.; Zhou, J. Angew. Chem. Int. Ed. 2013, 52, 3756. doi: 10.1002/anie.201210172 doi: 10.1002/anie.201210172
8. [8]
  Hemmila, I.; Webb, S. Drug Discovery Today1997, 2, 373. doi: 10.1016/s1359-6446(97)01080-5 doi: 10.1016/s1359-6446(97)01080-5
9. [9]
  Ward, M. D. Coord. Chem. Rev.2010, 254, 2634. doi: 10.1016/j.ccr.2009.12.001 doi: 10.1016/j.ccr.2009.12.001
10. [10]
  Vigato, R. A.; Peruzzo, V.; Tamburini, S. Coord. Chem. Rev. 2009, 253, 1099. doi: 10.1016/j.ccr.2008.07.013 doi: 10.1016/j.ccr.2008.07.013
11. [11]
  Wen, V.; Zhao, Y.; Wang, L.; Zhang, M.; Gao, D. J. Rare Earths 2007, 25, 679. doi: 10.1016/s1002-0721(08)60006-x doi: 10.1016/s1002-0721(08)60006-x
12. [12]
  Brayshaw, P. A.; Bünzli, J. C. G.; Froidevaux, P.; Harrowfield, J. M.; Kim, Y.; Sobolev, A. N. Inorg. Chem. 1995, 34, 2068. doi: 10.1021/ic00112a019 doi: 10.1021/ic00112a019
13. [13]
  Jankolovits, J.; Andolina, C. M.; Kampf, J. W.; Raymond, K. N.; Pecoraro, V. L. Angew. Chem. Int. Ed. 2011, 50, 9660. doi: 10.1002/anie.201103851 doi: 10.1002/anie.201103851
14. [14]
  Yang, X. P.; Jones, R. A.; Huang, S. M. Coord. Chem. Rev. 2014, 273, 63. doi: 10.1016/j.ccr.2013.11.012 doi: 10.1016/j.ccr.2013.11.012
15. [15]
  Yang, X. P.; Schipper, D.; Jones, R. A.; Lytwak, L. A.; Holliday, B. J.; Huang, S. M. J. Am. Chem. Soc.2013, 135, 8468. doi: 10.1021/ja4031243 doi: 10.1021/ja4031243
16. [16]
  Yang, X. P.; Jones, R. A. J. Am. Chem. Soc. 2005, 127, 7686. doi: 10.1021/ja051292c doi: 10.1021/ja051292c
17. [17]
  Yang, X. P.; Jones, R. A.; Wong, W. K. Dalton Trans. 2008, 1676. doi: 10.1039/b801513a doi: 10.1039/b801513a
18. [18]
  Lo, W. K.; Wong, W. K.; Wong, W. Y.; Guo, J.; Yeung, K. T.; Cheng, Y. K.; Yang, X. P.; Jones, R. A. Inorg.Chem. 2006, 45, 9315. doi: 10.1021/ic0610177 doi: 10.1021/ic0610177
19. [19]
  Yang, X. P.; Jones, R. A.; Wong, W. K.; Lynch, V.; Oye, M. M.; Holmes, A. L. Chem. Commun. 2006, 1836. doi: 10.1039/b518128c doi: 10.1039/b518128c
20. [20]
  Yang, X. P.; Chan, C.; Lam, D.; Schipper, D.; Stanley, J. M.; Chen, X.; Jones, R. A.; Holliday, B. J.; Wong, W. K.; Chen, S. C.; et al. Dalton Trans. 2012, 41, 11449. doi: 10.1039/c2dt31268a doi: 10.1039/c2dt31268a
21. [21]
  Lam, F.; Xu, J. X.; Chan, K. S. J. Org. Chem. 1996, 61, 8414. doi: 10.1021/jo961020f doi: 10.1021/jo961020f
22. [22]
  Meshkova, S. B.; Topilova, Z. M.; Bolshoy, D. V.; Beltyukova, S. V.; Tsvirko, M. P.; Venchikov, V. Y.; Ya, V. Acta Phys. Pol. A 1999, 95, 983. doi: 10.12693/aphyspola.95.983 doi: 10.12693/aphyspola.95.983
23. [23]
  Klink, S. I.; Grave, L.; Reinhoudt, D. N.; van Veggel, F. C. J. M. J. Phys. Chem. A 2000, 104, 5457. doi: 10.1021/jp994286+ doi: 10.1021/jp994286+
24. [24]
  Bünzli, J. C. G.; Piguet, C. Chem. Soc. Rev. 2005, 34, 1048. doi: 10.1039/b406082m doi: 10.1039/b406082m
25. [25]
  Shavaleev, N. M.; Accorsi, G.; Virgili, D.; Bell, D. R.; Lazarides, T.; Calogero, G.; Armaroli, N.; Ward, M. D. Inorg. Chem. 2005, 44, 61. doi: 10.1021/ic048875s doi: 10.1021/ic048875s
26. [26]
  Horrocks, W. D.; Bolender, J. P.; Smith, W. D.; Supkowski, R. M. J. Am. Chem. Soc. 1997, 119, 5972. doi: 10.1021/ja964421l doi: 10.1021/ja964421l
27. [27]
  Reinhard, C.; Gudel, H. U.Inorg. Chem. 2002, 41, 1048. doi: 10.1021/ic0108484 doi: 10.1021/ic0108484
1. [1]
  Hao Jiang , Yuan-Yuan He , Hai-Chao Liang , Meng-Jia Shang , Han-Han Lu , Chun-Hua Liu , Yin-Shan Meng , Tao Liu , Yuan-Yuan Zhu . Tuning lanthanide luminescence from bipyridine-bis(oxazoline/thiazoline) tetradentate ligands. Chinese Journal of Structural Chemistry, 2024, 43(9): 100354-100354. doi: 10.1016/j.cjsc.2024.100354
2. [2]
  Chun-Yun Ding , Ru-Yuan Zhang , Yu-Wu Zhong , Jiannian Yao . Binary and heterostructured microplates of iridium and ruthenium complexes: Preparation, characterization, and thermo-responsive emission. Chinese Journal of Structural Chemistry, 2024, 43(10): 100393-100393. doi: 10.1016/j.cjsc.2024.100393
3. [3]
  Pengfei Li , Chulin Qu , Fan Wu , Hu Gao , Chengyan Zhao , Yue Zhao , Zhen Shen . Robust free-base and metalated corrole radicals with reduction-induced emission. Chinese Chemical Letters, 2025, 36(2): 110292-. doi: 10.1016/j.cclet.2024.110292
4. [4]
  Pan Liu , Yanming Sun , Alberto J. Fernández-Carrión , Bowen Zhang , Hui Fu , Lunhua He , Xing Ming , Congling Yin , Xiaojun Kuang . Bismuth-based halide double perovskite Cs₂KBiCl₆: Disorder and luminescence. Chinese Chemical Letters, 2024, 35(5): 108641-. doi: 10.1016/j.cclet.2023.108641
5. [5]
  Yan Cheng , Hua-Peng Ruan , Yan Peng , Longhe Li , Zhenqiang Xie , Lang Liu , Shiyong Zhang , Hengyun Ye , Zhao-Bo Hu . Magnetic, dielectric and luminescence synergetic switchable effects in molecular material [Et₃NCH₂Cl]₂[MnBr₄]. Chinese Chemical Letters, 2024, 35(4): 108554-. doi: 10.1016/j.cclet.2023.108554
6. [6]
  Yinling HOU , Jia JI , Hong YU , Xiaoyun BIAN , Xiaofen GUAN , Jing QIU , Shuyi REN , Ming FANG . A rhombic Dy₄-based complex showing remarkable single-molecule magnet behavior. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 605-612. doi: 10.11862/CJIC.20240251
7. [7]
  Fan Wu , Shaoyang Wu , Xin Ye , Yurong Ren , Peng Wei . Research progress of high-entropy cathode materials for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(4): 109851-. doi: 10.1016/j.cclet.2024.109851
8. [8]
  Fengshun Wang , Huachao Ji , Zefei Wu , Kang Chen , Wenqi Gao , Chen Wang , Longlu Wang , Jianmei Chen , Dafeng Yan . The advanced development of one-dimensional transition metal dichalcogenide nanotubes: From preparation to application. Chinese Chemical Letters, 2025, 36(5): 109898-. doi: 10.1016/j.cclet.2024.109898
9. [9]
  Qiao Wang , Ziling Jiang , Chuang Yu , Liping Li , Guangshe Li . Research progress of inorganic sodium ion conductors for solid-state batteries. Chinese Chemical Letters, 2025, 36(6): 110006-. doi: 10.1016/j.cclet.2024.110006
10. [10]
  Yupeng Liu , Hui Wang , Songnan Qu . Review on near-infrared absorbing/emissive carbon dots: From preparation to multi-functional application. Chinese Chemical Letters, 2025, 36(5): 110618-. doi: 10.1016/j.cclet.2024.110618
11. [11]
  Xiangshuai Li , Jian Zhao , Li Luo , Zhuohao Jiao , Ying Shi , Shengli Hou , Bin Zhao . Visual and portable detection of metronidazole realized by metal-organic framework flexible sensor and smartphone scanning. Chinese Chemical Letters, 2024, 35(10): 109407-. doi: 10.1016/j.cclet.2023.109407
12. [12]
  Zhu Shu , Xin Lei , Yeye Ai , Ke Shao , Jianliang Shen , Zhegang Huang , Yongguang Li . ATP-induced supramolecular assembly based on chromophoric organic molecules and metal complexes. Chinese Chemical Letters, 2024, 35(11): 109585-. doi: 10.1016/j.cclet.2024.109585
13. [13]
  Wen-Jun Xia , Yong-Jiang Wang , Yun-Fei Cao , Cai Sun , Xin-Xiong Li , Yan-Qiong Sun , Shou-Tian Zheng . A luminescent folded S-shaped high-nuclearity Eu₁₉-oxo-cluster embedded polyoxoniobate for information encryption. Chinese Chemical Letters, 2025, 36(2): 110248-. doi: 10.1016/j.cclet.2024.110248
14. [14]
  Xinhui Fang , Xinrui Wang , Bin Ding . Applications of luminescent metal-organic frameworks as pioneering biosensors for biological and chemical detection. Chinese Chemical Letters, 2025, 36(8): 110453-. doi: 10.1016/j.cclet.2024.110453
15. [15]
  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
16. [16]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188
17. [17]
  Yingyue ZHANG , Liuqing KANG , Yating YANG , Xiaofen GUAN , Wenmin WANG . Crystal structure and antibacterial activity of two Gd₂ complexes based on polydentate Schiff-base ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1867-1877. doi: 10.11862/CJIC.20250100
18. [18]
  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
19. [19]
  Qiuyu Ming , Huijun Jiang , Zhihao Zhang . A Sightseeing Tour of Folic Acid Processing Plant. University Chemistry, 2024, 39(9): 11-15. doi: 10.12461/PKU.DXHX202404092
20. [20]
  Ke Wu , Xiuqin Ruan , Shuolei Jia , Enyuan Wang , Qingfa Zhou . DABCO-catalyzed [3+4] annulations of Schiff bases with α-substituted allenes: Construction of functionalized benzazepine derivatives. Chinese Chemical Letters, 2025, 36(7): 110646-. doi: 10.1016/j.cclet.2024.110646

Get Citation

PDF

XML

Metrics

PDF Downloads(9)
Abstract views(597)
HTML views(83)

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