Citation: Mengxue Zhou, Ning Ren, Jianjun Zhang. Crystal Structure, Thermal Decomposition Mechanism and Properties of Lanthanide Supramolecular Complexes Based on 2, 4, 6-Trimethylbenzoic Acid and 5, 5'-Dimethyl-2, 2'-bipyridine[J]. Acta Physico-Chimica Sinica, ;2021, 37(10): 200407. doi: 10.3866/PKU.WHXB202004071 shu

Crystal Structure, Thermal Decomposition Mechanism and Properties of Lanthanide Supramolecular Complexes Based on 2, 4, 6-Trimethylbenzoic Acid and 5, 5'-Dimethyl-2, 2'-bipyridine

Mengxue Zhou ^{1, 2} ,
Ning Ren ^3,, ,
Jianjun Zhang ^{1, 2,,}

1.
Testing and Analysis Center, Hebei Normal University, Shijiazhuang 050024, China
2.
College of Chemistry & Material Science, Hebei Normal University, Shijiazhuang 050024, China
3.
College of Chemical Engineering & Material, Hebei Key Laboratory of Heterocyclic Compounds, Handan University, Handan 056005, Hebei Province, China

Corresponding author: Ning Ren, ningren9@163.com Jianjun Zhang, jjzhang6@126.com
Received Date: 27 April 2020
Revised Date: 15 May 2020
Accepted Date: 15 May 2020
Available Online: 20 May 2020
Fund Project: the National Natural Science Foundation of China 21803016

Six ternary lanthanide complexes formulated as [Ln(2, 4, 6-TMBA)₃(5, 5'-DM-2, 2'-bipy)]₂ (Ln = Pr 1, Nd 2, Sm 3, Eu 4, Gd 5, Dy 6; 2, 4, 6-TMBA = 2, 4, 6-trimethylbenzoate; 5, 5'-DM-2, 2'-bipy = 5, 5'-dimethyl-2, 2'-bipyridine) have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, etc. The results of crystal diffraction analysis show that complexes 1–6 are binuclear units, crystallizing in the triclinic Pī space group. Complexes 1–5 are isostructural, and each of the central metal ions has a coordination number of 9. The asymmetric unit of complexes 1–5 consists of one Ln³⁺, one 5, 5'-DM-2, 2'-bipy ligand, and three 2, 4, 6-TMBA^- moieties with three coordination modes: chelation bidentate, bridging bidentate, and bridging tridentate. The coordination geometry of Ln³⁺ is distorted monocapped square antiprismatic. The binuclear units of complexes 1–5 form a one-dimensional (1D) supramolecular chain along the c-axis via π–π stacking interactions between the 2, 4, 6-trimethylbenzoic acid rings. The 1D chains are linked to form a supramolecular two-dimensional (2D) sheet in the bc plane via π–π stacking interactions between the pyridine rings. Although the molecular formulae of complex 6 and complexes 1–5 are similar, the coordination environment of the lanthanide ions is different in the two cases. The asymmetric unit of complex 6 contains a Dy³⁺ ion coordinated by a bidentate 5, 5'-DM-2, 2'-bipy and three 2, 4, 6-TMBA^- ligands adopting bidentate and bridging bidentate coordination modes. The Dy³⁺ metal center has a coordination number of 8, with distorted square antiprismatic molecular geometry. The binuclear molecule of 6 is assembled into a six-nuclear unit by π–π weak staking interactions between two 5, 5'-DM-2, 2'-bipy ligands; then, adjacent six-nuclear units form a 1D chain via offset π–π interactions between 5, 5'-DM-2, 2'-bipy ligands on different adjacent units. The adjacent 1D chains are linked by C―H···O hydrogen bonding interactions to form a 2D supramolecular structure. The thermal stability and thermal decomposition mechanism of all the complexes are investigated by the combination of thermogravimetry and infrared spectroscopy (TG/FTIR) techniques under a simulated air atmosphere in the temperature range of 298–973 K at a heating rate of 10 K·min^-1. Thermogravimetric studies show that this series of complexes have excellent thermal stability. During the thermal decomposition of the complex, the neutral ligand is lost first, followed by the acid ligand, and finally, the complex is decomposed into rare earth oxides. The three-dimensional infrared results are consistent with the thermogravimetric results. The photoluminescence spectra of complex 4 show the strong characteristic luminescence of Eu³⁺. The five typical emission peaks at 581, 591, 621, 651, and 701 nm correspond to the ⁵D₀ → ⁷F₀, ⁵D₀ → ⁷F₁, ⁵D₀ → ⁷F₂, ⁵D₀ → ⁷F₃, and ⁵D₀ → ⁷F₄ electronic transitions of Eu³⁺, respectively. The emission at 621 nm is due to the electric dipole transition ⁵D₀ → ⁷F₂, while that at 591 nm is assigned to the ⁵D₀ → ⁷F₁ the magnetic dipole transition. The lifetime (τ) of complex 4 is calculated as 1.15 ms based on the equation τ = (B₁τ₁² + B₂τ₂²))/(B₁τ₁ + B₂τ₂), and the intrinsic quantum yield is calculated to be 45.1%. Further, the magnetic properties of complex 6 in the temperature range of 2–300 K are studied under an applied magnetic field of 1000 Oe.
- Lanthanide supramolecular complexes,
- Crystal structure,
- Thermal behavior,
- Luminescence spectrum,
- 2, 4, 6-Trimethylbenzoic acid
1. [1]
  Janicki, R.; Mondry, A.; Starynowicz, P. Coordin. Chem. Rev. 2017, 340, 98. doi: 10.1016/j.ccr.2016.12.001 doi: 10.1016/j.ccr.2016.12.001
2. [2]
  Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. Chem. Soc. Rev. 2009, 38 (5), 1330. doi: 10.1039/b802352m doi: 10.1039/b802352m
3. [3]
  Ahmed, Z.; Iftikhar, K. Inorg. Chem. 2015, 54 (23), 11209. doi: 10.1021/acs.inorgchem.5b01630 doi: 10.1021/acs.inorgchem.5b01630
4. [4]
  Bradberry, S. J.; Savyasachi, A. J.; Martinez-Calvo, M.; Gunnlaugsson, T. Coordin. Chem. Rev. 2014, 273-274, 226. doi: 10.1016/j.ccr.2014.03.023 doi: 10.1016/j.ccr.2014.03.023
5. [5]
  Bunzli, J. C.; Piguet, C. Chem. Soc. Rev. 2005, 34 (12), 1048. doi: 10.1039/b406082m doi: 10.1039/b406082m
6. [6]
  Hiller, M.; Krieg, S.; Ishikawa, N.; Enders, M. Inorg. Chem. 2017, 56 (24), 15285. doi: 10.1021/acs.inorgchem.7b02704 doi: 10.1021/acs.inorgchem.7b02704
7. [7]
  Lin, P. H.; Burchell, T. J.; Clerac, R.; Murugesu, M. Angew. Chem. Int. Ed. Engl. 2008, 47 (46), 8848. doi: 10.1002/anie.200802966 doi: 10.1002/anie.200802966
8. [8]
  Reis, S. G.; Briganti, M.; Soriano, S.; Guedes, G. P.; Calancea, S.; Tiseanu, C. Inorg. Chem. 2016, 55 (22), 11676. doi: 10.1021/acs.inorgchem.6b01616 doi: 10.1021/acs.inorgchem.6b01616
9. [9]
  Rinehart, J. D.; Long, J. R. Chem. Sci. 2011, 2 (11), 2078. doi: 10.1039/c1sc00513h doi: 10.1039/c1sc00513h
10. [10]
  Wang, G.; Song, T.; Fan, Y.; Xu, J.; Wang, M.; Wang, L. Inorg. Chem. Commun. 2010, 13 (1), 95. doi: 10.1016/j.inoche.2009.10.026 doi: 10.1016/j.inoche.2009.10.026
11. [11]
  Niu, Y.; Xu, Q.; Wang, Y.; Li, Z.; Lu, J.; Ma, P. Dalton Trans. 2018, 47 (29), 9677. doi: 10.1039/c8dt01243a doi: 10.1039/c8dt01243a
12. [12]
  Wang, W.; Wang, X.; Zhou, S.; Xu, X.; Du, J.; Zhang, L. Inorg. Chem. 2018, 57 (16), 10390. doi: 10.1021/acs.inorgchem.8b01556 doi: 10.1021/acs.inorgchem.8b01556
13. [13]
  Li, Y. J.; Yan, B. Inorg. Chem. 2009, 48 (17), 8276. doi: 10.1021/ic900971h doi: 10.1021/ic900971h
14. [14]
  Heffern, M. C.; Matosziuk, L. M.; Meade, T. J. Chem. Rev. 2014, 114 (8), 4496. doi: 10.1021/cr400477t doi: 10.1021/cr400477t
15. [15]
  Bünzli, J. C. G. J. Lumin. 2016, 170, 866. doi: 10.1016/j.jlumin.2015.07.033 doi: 10.1016/j.jlumin.2015.07.033
16. [16]
  Zhao, Q. Q.; Zhu, M. M.; Ren, N.; Zhang, J. J. J. Mol. Struct. 2017, 1149, 171. doi: 10.1016/j.molstruc.2017.07.080 doi: 10.1016/j.molstruc.2017.07.080
17. [17]
  Monteiro, J. H. S. K.; Sigoli, F. A.; de Bettencourt-Dias, A. Can. J. Chem. 2018, 96 (9), 859. doi: 10.1139/cjc-2017-0436 doi: 10.1139/cjc-2017-0436
18. [18]
  Jin, C. W.; Wang, Y.; Ren, N.; Geng, L. N.; Zhang, J. J. J. Chem. Thermodyn. 2016, 103, 181. doi: 10.1016/j.jct.2016.08.011 doi: 10.1016/j.jct.2016.08.011
19. [19]
  Wu, J.; Li, H.; Ren, N.; Zhang, J.; Wang, S. J. Rare Earths 2016, 34 (11), 1083. doi: 10.1016/s1002-0721(16)60138-2 doi: 10.1016/s1002-0721(16)60138-2
20. [20]
  Xia, C. K.; Sun, W.; Min, Y. Y.; Yang, K.; Wu, Y. L. Polyhedron 2018, 141, 377. doi: 10.1016/j.poly.2017.11.011 doi: 10.1016/j.poly.2017.11.011
21. [21]
  Utochnikova, V. V.; Grishko, A.; Vashchenko, A.; Goloveshkin, A.; Averin, A.; Kuzmina, N. Eur. J. Inorg. Chem. 2017, 2017 (48), 5635. doi: 10.1002/ejic.201700896 doi: 10.1002/ejic.201700896
22. [22]
  He, S. M.; Sun, S. J.; Zheng, J. R.; Zhang, J. J. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2014, 123, 211. doi: 10.1016/j.saa.2013.12.023 doi: 10.1016/j.saa.2013.12.023
23. [23]
  Carter, K. P.; Pope, S. J. A.; Cahill, C. L. CrystEngComm 2014, 16 (10), 1873. doi: 10.1039/c3ce42267d doi: 10.1039/c3ce42267d
24. [24]
  Zapała, L.; Kosińska, M.; Woźnicka, E.; Byczyński, Ł.; Zapała, W.; Kalembkiewicz, J. J. Anal. Appl. Pyrol. 2017, 123, 1. doi: 10.1016/j.jaap.2017.01.010 doi: 10.1016/j.jaap.2017.01.010
25. [25]
  Gao, H. L.; Huang, S. X.; Zhou, X. P.; Liu, Z.; Cui, J. Z. Dalton Trans. 2018, 47 (10), 3503. doi: 10.1039/c8dt00063h doi: 10.1039/c8dt00063h
26. [26]
  Kariem, M.; Yawer, M.; Kumar, M.; Nawaz Sheikh, H.; Sood, P.; Kolekar, S. S. J. Solid. State. Chem. 2017, 255, 61. doi: 10.1016/j.jssc.2017.08.001 doi: 10.1016/j.jssc.2017.08.001
27. [27]
  Shen, P. P.; Zhu, M. M.; Ren, N.; Zhang, J. J.; Wang, S. P. Appl. Organomet. Chem. 2017, 31 (12), e3886, doi: 10.1002/aoc.3886 doi: 10.1002/aoc.3886
28. [28]
  Xie, H.; Lu, G. J. Rare Earths 2013, 31 (6), 639. doi: 10.1016/s1002-0721(12)60334-2 doi: 10.1016/s1002-0721(12)60334-2
29. [29]
  Zhao, Y. F.; Chu, H. B.; Bai, F.; Gao, D. Q.; Zhang, H. X.; Zhou, Y. S. J. Organomet. Chem. 2012, 716, 167. doi: 10.1016/j.jorganchem.2012.06.031 doi: 10.1016/j.jorganchem.2012.06.031
30. [30]
  Shen, C. Q.; Yan, T. L.; Wang, Y. T.; Ye, Z. J.; Xu, C. J.; Zhou, W. J. J. Lumin. 2017, 184, 48. doi: 10.1016/j.jlumin.2016.12.018 doi: 10.1016/j.jlumin.2016.12.018
31. [31]
  Zhu, M. M.; Ren, N.; Zhang, J. J. Inorg. Chim. Acta 2018, 480, 140. doi: 10.1016/j.ica.2018.05.022 doi: 10.1016/j.ica.2018.05.022
32. [32]
  Bünzli, J. C. G.; Chauvin, A. S.; Kim, H. K.; Deiters, E.; Eliseeva, S. V. Coordin. Chem. Rev. 2010, 254 (21-22), 2623. doi: 10.1016/j.ccr.2010.04.002 doi: 10.1016/j.ccr.2010.04.002
33. [33]
  Wei, X. H.; Yang, L. Y.; Liao, S. Y.; Zhang, M.; Tian, J. L.; Du, P. Y. Dalton Trans. 2014, 43 (15), 5793. doi: 10.1039/c3dt53112k doi: 10.1039/c3dt53112k
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