Citation: Xiao-Bo YU, Zhao CHEN, Yuan-Jie MA, Ling LI, Wen-Ting CHANG, Bo LI, Cheng-Hui ZENG. Synthesis of Highly Luminescent LnMOFs through Structural Regulation[J]. Chinese Journal of Structural Chemistry, ;2022, 41(3): 220327. doi: 10.14102/j.cnki.0254-5861.2021-0013 shu

Synthesis of Highly Luminescent LnMOFs through Structural Regulation

Xiao-Bo YU ^{a, b} ,
Zhao CHEN ^{a, b} ,
Yuan-Jie MA ^{a, b} ,
Ling LI ^{a, b} ,
Wen-Ting CHANG ^{a, b} ,
Bo LI ^{a, b} ,
Cheng-Hui ZENG ^{a, b,,}

a.
College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China
b.
Jiangxi Yuean Superfine Met Co Ltd, Ganzhou, Jiangxi 341000, China

Corresponding author: Cheng-Hui ZENG, chenghuizeng@jxnu.edu.cn
Received Date: 19 November 2021
Accepted Date: 25 November 2021

Fund Project: the National Natural Science Foundation of China 51962008Natural Science Foundation of Jiangxi Province 20202BABL203018

Figures(5)

Two series of three dimensional (3D) lanthanide metal-organic frameworks (LnMOFs) of [Ln(tftpa)_1.5(phen)(H₂O)]_n (Ln = Sm 1a, Eu 1b, Tb 1c, Dy 1d, H₂tftpa = tetrafluoroterephthalic acid, phen = 1, 10-phenanthrolin) and [Ln(tftpa)_1.5(bpy)(H₂O)]_n (Ln = Sm 2a, Eu 2b, Tb 2c, Dy 2d, bpy = 2, 2΄-bipyridine) are obtained by structural regulation. Results reveal that the 3D LnMOFs show high water- and thermal-stability. Interestingly, through selecting the perfluorinated ligand, and using bpy as an auxiliary ligand to hold back the solvents near to the lanthanide ions, 2b, and 2c show high luminescence quantum yield (QY) of 74.50% and 60.03%, respectively. In order to further improve the luminescence QY, the auxiliary ligand of phen with larger conjugation and more rigid structure is synthesized to replace bpy, and fortunately, higher luminescence QY of 80.73% (1b) and 75.17% (1c) are realized.
- highly luminescent,
- LnMOFs,
- structural regulation,
- luminescence quantum yield
1. [1]
  (a) Ghasempour, H.; Wang, K. Y.; Powell, J. A.; ZareKarizi, F.; Lv, X. L.; Morsali, A.; Zhou, H. C. Metal-organic frameworks based on multicarboxylate linkers. Coord. Chem. Rev. 2021, 426, 10.1016/j. ccr. 2020.213542. (b) Wang, X. T.; Wei, W.; Zhang, K.; Du, S. W. Detection of diethyl ether by a europium MOF through fluorescence enhancement. . Chin. J. Struct. Chem. 2021, 40, 369–375.
2. [2]
  Liao, P. Q.; Huang, N. Y.; Zhang, W. X.; Zhang, J. P.; Chen, X. M. Controlling guest conformation for efficient purification of butadiene. Science 2017, 356, 1193–1196. doi: 10.1126/science.aam7232
3. [3]
  (a) Li, C.; Zeng, C.; Chen, Z.; Jiang, Y.; Yao, H.; Yang, Y.; Wong, W. T. Luminescent lanthanide metal-organic framework test strip for immediate detection of tetracycline antibiotics in water. J. Hazard. Mater. 2020, 384, 121498. (b) Liu, M.; Li, H.; Bai, L.; Zheng, K.; Zhao, Z.; Chen, Z.; Ng, S. W.; Ding, L.; Zeng, C. Real-time and visual sensing devices based on pH-control assembled lanthanide-barium nano-cluster. J. Hazard. Mater. 2021, 413, 125291–125291. (c) Liu, M.; Li, Z.; Xiong, J.; Jiang, Y.; Tang, T.; Qiu, J.; Yao, J.; Ng, S. W.; Zeng, C. Structure regulation for ultra-high luminescence quantum yield lanthanide complex and simultaneous detection of cancer marker and ferrous ion. . J. Rare Earths 2021, 39, 1194–1203.
4. [4]
  Ma, Y. J.; Hu, J. X.; Han, S. D.; Pan, J.; Li, J. H.; Wang, G. M. Manipulating on/off single-molecule magnet behavior in a Dy(III)-based photochromic complex. J. Am. Chem. Soc. 2020, 142, 2682–2689. doi: 10.1021/jacs.9b13461
5. [5]
  Zhang, Q.; Wei, W. J.; Li, Q.; Pan, J.; Han, S. D.; Hu, J. X.; Wang, G. M. Light enhanced proton conductivity in a terbium phosphonate photochromic chain complex. Sci. China Chem. 2021, 10.1007/s11426-11021-19976-11427.
6. [6]
  Muldoon, P. F.; Collet, G.; Eliseeva, S. V.; Luo, T. Y.; Petoud, S.; Rosi, N. L. Ship-in-a-bottle preparation of long wavelength molecular antennae in lanthanide metal-organic frameworks for biological imaging. J. Am. Chem. Soc. 2020, 142, 8776–8781. doi: 10.1021/jacs.0c01426
7. [7]
  (a) Cao, C. C.; Chen, C. X.; Wei, Z. W.; Qiu, Q. F.; Zhu, N. X.; Xiong, Y. Y.; Jiang, J. J.; Wang, D.; Su, C. Y. Catalysis through dynamic spacer installation of multivariate functionalities in metal-organic frameworks. J. Am. Chem. Soc. 2019, 141, 2589–2593. (b) Dhakshinamoorth, A.; Asiri, A. M.; Garcia, H. 2D metal-organic frameworks as multifunctional materials in heterogeneous catalysis and electro/photocatalysis. Adv. Mater. 2019, 31, 1900617. (c) Zhang, X. D.; Huang, L. R.; Wu, J. X.; Gu, Z. Y. Enhancing selectivity through decrypting the uncoordinated zirconium sites in MOF electrocatalysts. . Chem. Commun. 2021, 57, 5191–5194.
8. [8]
  (a) Chen, X.; Xu, Y.; Li, H. Lanthanide organic/inorganic hybrid systems: efficient sensors for fluorescence detection. Dyes Pigments 2020, 178, 108386. (b) Ren, Y. W.; Hu, H. N.; Zhang, J.; Zhuang, X. J.; Li, D. P.; Li, Y. X. Characterization and DNA interaction of lanthanide complexes based on thiourea ligand. . Chin. J. Struct. Chem. 2021, 40, 47–54.
9. [9]
  Chen, Z. B.; Chen, B. B.; Cheng, J. W. Luminescent lanthanide-titanium-organic compound constructed by tetra-nuclear Ln-Ti building units and diphenylglycolic acid. . Chin. J. Struct. Chem. 2021, 40, 182–186.
10. [10]
  (a) Yan, B.; Liang, R.; Zheng, K.; Li, R.; Ma, P.; Wang, J.; Niu, J. Multinuclear lanthanide-implanted tetrameric dawson-type phosphotungstates with switchable luminescence behaviors induced by fast photochromism. . Inorg. Chem. 2021, 60, 8164–8172. (b) Fordham, S.; Wang, X.; Bosch, M.; Zhou, H. C. In Lanthanide Metal-Organic Frameworks. Cheng, P., Ed. 2015, 163, pp 1–27.
11. [11]
  Lima, N. B. D.; Goncalves, S. M. C.; Junior, S. A.; Simas, A. M. A comprehensive strategy to boost the quantum yield of luminescence of europium complexes. . Sci. Rep. 2013, 3, 2395. doi: 10.1038/srep02395
12. [12]
  Hirai, Y.; Nakanishi, T.; Kitagawa, Y.; Fushimi, K.; Seki, T.; Ito, H.; Hasegawa, Y. Triboluminescence of lanthanide coordination polymers with face-to-face arranged substituents. . Angew. Chem. Int. Ed. 2017, 56, 7171–7175. doi: 10.1002/anie.201703638
13. [13]
  (a) Winkless, L.; Tan, R. H. C.; Zheng, Y.; Motevalli, M.; Wyatt, P. B.; Gillin, W. P. Quenching of Er(III) luminescence by ligand C–H vibrations: implications for the use of erbium complexes in telecommunications. . Appl. Phys. Lett. 2006, 89, 111115. (b) Armelao, L.; Quici, S.; Barigelletti, F.; Accorsi, G.; Bottaro, G.; Cavazzini, M.; Tondello, E. Design of luminescent lanthanide complexes: from molecules to highly efficient photo-emitting materials. . Coord. Chem. Rev. 2010, 254, 487–505.
14. [14]
  Lian, X.; Zhao, D.; Cui, Y.; Yang, Y.; Qian, G. A near infrared luminescent metal-organic framework for temperature sensing in the physiological range. . Chem. Commun. 2015, 51, 17676–17679. doi: 10.1039/C5CC07532G
15. [15]
  Sabbatini, N.; Guardigli, M.; Lehn, J. M. Luminescent lanthanide complexes as photochemical supramolecular devices. Coord. Chem. Rev. 1993, 123, 201–228. doi: 10.1016/0010-8545(93)85056-A
16. [16]
  Moudam, O.; Rowan, B. C.; Alamiry, M.; Richardson, P.; Richards, B. S.; Jones, A. C.; Robertson, N. Europium complexes with high total photoluminescence quantum yields in solution and in PMMA. . Chem. Commun. 2009, 6649–6651.
17. [17]
  Zou, M.; Xia, X.; Jiang, Y.; Peng, J.; Jia, Z.; Wang, X.; Li, F. Strengthened perovskite/fullerene interface enhances efficiency and stability of inverted planar perovskite solar cells via a tetrafluoroterephthalic acid interlayer. . Acs Appl. Mater. Interfaces 2019, 11, 33515–33524. doi: 10.1021/acsami.9b12961
18. [18]
  Yu, H. H.; Chi, J. Q.; Su, Z. M.; Li, X.; Sun, J.; Zhou, C.; Hu, X. L.; Liu, Q. A water-stable terbium metal-organic framework with functionalized ligands for the detection of Fe³⁺ and Cr₂O₇²⁻ ions in water and picric acid in seawater. . CrystEngComm 2020, 22, 3638–3643. doi: 10.1039/D0CE00430H
19. [19]
  Yu, H.; Liu, Q.; Li, J.; Su, Z. M.; Li, X.; Wang, X.; Sun, J.; Zhou, C.; Hu, X. A dual-emitting mixed-lanthanide MOF with high water-stability for ratiometric fluorescence sensing of Fe³⁺ and ascorbic acid. . J. Mater. Chem. C 2021, 9, 562–568.
20. [20]
  (a) Xu, Y.; Li, X. X.; Wang, H. X.; Liu, H. R.; Chen, Q.; Dou, Q. Synthesis, crystal structure and luminescence of one-dimensional homochiral terbium(III) coordination polymers. . Chin. J. Struct. Chem. 2020, 39, 1044–1050. (b) Wang, Z. Q.; Pan, X.; Lu, Y. L.; Li, Y. Y.; Yang, Y. P.; Xin, X. L.; Jin, Q. H. Crystal structures, terahertz spectra and dye adsorption performance of three lanthanide-bisphosphonate complexes containing keggin polyoxometalates. Chin. J. Struct. Chem. 2021, 40, 615–624.
21. [21]
  Korostei, Y. S.; Pushkarev, V. E.; Tolbin, A. Y.; Dzuban, A. V.; Chernyak, A. V.; Konev, D. V.; Medvedeva, T. O.; Talantsev, A. D.; Sanina, N. A.; Tomilova, L. G. Sandwich quadruple-decker binuclear lanthanide(III) complexes based on clamshell-type phthalocyanine ligand: synthesis and physicochemical studies. Dyes Pigments 2019, 170, 107648.
22. [22]
  (a) He, X.; Liu, Y.; Lv, Y.; Dong, Y.; Hu, G.; Zhou, S.; Xu, Y. L- and D-LnZn(IN)₃(C₂H₄O₂)_n (Ln = Eu, Sm, and Gd): chiral enantiomerically 3D 3d–4f coordination polymers constructed by interesting butterfly-like building units and -[Ln-O-Zn]_n-helices. . Inorg. Chem. 2016, 55, 2048–2054. (b) Kumar, M.; Kariem, M.; Sheikh, H. N.; Frontera, A.; Seth, S. K.; Jassal, A. K. A series of 3D lanthanide coordination polymers decorated with a rigid 3, 5-pyridinedicarboxylic acid linker: syntheses, structural diversity, DFT study, Hirshfeld surface analysis, luminescence and magnetic properties. . Dalton Trans. 2018, 47, 12318–12336.
23. [23]
  (a) Zheng, K.; Liu, Z.; Jiang, Y.; Guo, P.; Li, H.; Zeng, C.; Ng, S. W.; Zhong, S. Ultrahigh luminescence quantum yield lanthanide coordination polymer as a multifunctional sensor. . Dalton Trans. 2018, 47, 17432–17440. (b) Qian, X. Y.; Zhang, J. H.; Zhou, T. H.; Mao, J. G. Syntheses, crystal structures and luminescent properties of new lanthanide(III) organoarsonates. Dalton Trans. 2012, 41, 1229–1236. (c) Kumar, M.; Li, L. Q.; Zaręba, J. K.; Tashi, L.; Sahoo, S. C.; Nyk, M.; Liu, S. J.; Sheikh, H. N. Lanthanide contraction in action: structural variations in 13 lanthanide(III) thiophene-2, 5-dicarboxylate coordination polymers (Ln = La–Lu, except Pm and Tm) featuring magnetocaloric effect, slow magnetic relaxation, and luminescence-lifetime-based thermometry. . Cryst. Growth. Des. 2020, 20, 6430–6452. (d) Kumar, M.; Qiu, C. Q.; Zaręba, J. K.; Frontera, A.; Jassal, A. K.; Sahoo, S. C.; Liu, S. J.; Sheikh, H. N. Magnetic, luminescence, topological and theoretical studies of structurally diverse supramolecular lanthanide coordination polymers with flexible glutaric acid as a linker. . New J. Chem. 2019, 43, 14546–14564.
24. [24]
  (a) Zheng, K.; Liu, Z. Q.; Huang, Y.; Chen, F.; Zeng, C. H.; Zhong, S.; Ng, S. W. Highly luminescent Ln-MOFs based on 1, 3-adamantanediacetic acid as bifunctional sensor. . Sens. Actuators B Chem. 2018, 257, 705–713. (b) Tang, T.; Liu, M.; Chen, Z.; Wang, X.; Lai, C.; Ding, L.; Zeng, C. Highly sensitive luminescent lanthanide metal-organic framework sensor for L-kynurenine. . J. Rare Earths 2021, 10.1016/j. jre. 2021.1002. 1008. (c) Yang, Y. Q.; Tuo, L. Y.; Li, W. Synthesis, structure and properties of a new terbium(III) complex Tb₂(C₁₅H₁₁O₃)₆(2, 2'-bipy)₂. . Chin. J. Struct. Chem. 2020, 39, 1331–1336. (d) Yang, Y. Q.; Kuang, Y. F.; Zhu, X. M. Synthesis and fluorescent and magnetic properties of a new europium complex Eu(C₂₀H₁₄O₃N)₃(2, 2'-bipy)(H₂O)center dot H₂O. . . Chin. J. Struct. Chem. 2021, 40, 507–511. (e) Kumar, M.; Wu, L. H.; Kariem, M.; Franconetti, A.; Sheikh, H. N.; Liu, S. J.; Sahoo, S. C.; Frontera, A. A series of lanthanide-based metal-organic frameworks derived from furan-2, 5-dicarboxylate and glutarate: structure-corroborated density functional theory study, magnetocaloric effect, slow relaxation of magnetization, and luminescent properties. . Inorg. Chem. 2019, 58, 7760–7774.
25. [25]
  Li, M.; Takei, T.; Zhu, Q.; Kim, B. N.; Li, J. G. Morphology tailoring of ZnWO₄ crystallites/architectures and photoluminescence of the doped RE³⁺ ions (RE = Sm, Eu, Tb, and Dy). Inorg. Chem. 2019, 58, 9432–9442.
26. [26]
  Aquino, L. E. D. N.; Barbosa, G. A.; Ramos, J. D. L.; Giese, S. O. K.; Santana, F. S.; Hughes, D. L.; Nunes, G. G.; Fu, L.; Fang, M.; Poneti, G.; Carneiro Neto, A. N.; Moura Jr, R. T.; Ferreira, R. A. S.; Carlos, L. D.; Macedo, A. G.; Soares, J. F. Seven-coordinate Tb³⁺ complexes with 90% quantum yields: high-performance examples of combined singlet- and triplet-to-Tb³⁺ energy-transfer pathways. . Inorg. Chem. 2021, 60, 893–908.
27. [27]
  Zeng, C. H.; Meng, X. T.; Xu, S. S.; Han, L. J.; Zhong, S.; Jia, M. Y. A polymorphic lanthanide complex as selective Co²⁺ sensor and luminescent timer. . . Sens. Actuators B Chem. 2015, 221, 127–135.
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