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Crystal structures and thermal decomposition mechanism of four lanthanide complexes with halogen-benzoic acid and 1,10-phenanthroline

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Abstract

This paper describes syntheses and structure determination of four lanthanide complexes [Nd(2-Cl-4-FBA)3phen]2 (1, 2-Cl-4-FBA = 2-chloro-4-fluorobenzoate, phen = 1,10-phenanthroline), [Ln(2,5-DClBA)3phen]2 (Ln = Sm(2) and Tb(3), 2,5-DClBA = 2,5-dichlorobenzoate) and [Sm(2-Cl-4,5-DFBA)3(phen)(H2O)]2 (4, (2-Cl-4,5-DFBA = 2-chloro-4,5-difluorobenzoate). The complexes were characterized by elemental analysis, infrared and ultraviolet spectra, and X-ray single-crystal diffraction. In the molecular structures of 1–4, two Ln3+ ions are linked by four carboxyl groups, with two of them in a bridging bidentate mode and the other two in a bridging-chelating tridentate mode, forming four binuclear molecules. In addition, each Ln3+ ion is also chelated to one phen molecule and one carboxyl group in the complexes, except each Sm3+ ion in 4 which is bonded to one carboxyl group by unidentate mode and one H2O molecule. There are two different coordination polyhedrons for each Nd3+ ion in the two similar molecular structures of 1 and they are a distorted monocapped square antiprismatic and a distorted tricapped triangular prism conformation, respectively. The coordination polyhedron for each Ln3+ ion in 2–4 is a nine-coordinated distorted mono-capped square antiprismatic conformation. The complex 3 exhibits green luminescence under the radiation of UV light. The thermal decomposition behaviors of the complexes have been discussed by simultaneous TG/DSC-FTIR technique. The 3D surface graphs for the FTIR spectra of the evolved gases were recorded and the gaseous products were identified by the typical IR spectra obtained at different temperatures from the 3D surface graphs. Meanwhile, we discussed the non-isothermal kinetics of 1–4 by the integral isoconversional non-linear (NL-INT) method.

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References

  1. Li X, Shi Q, Sun DF, Bi WH, Cao R. Synthesis and characterization of a series of lanthanide complexes constructed from orotic acid. Eur J Inorg Chem, 2004 (13): 2747–2753

  2. Tian L, Ren N, Zhang JJ, Liu HM, Bai JH, Ye HM, Sun SJ. Synthesis, crystal structure, luminescence and thermal decomposition kinetics of Eu(III) complex with 2,4-dichlorobenzoic acid and 2, 20-bipyridine. Inorg Chim Acta, 2009, 362: 3388–3394

    Article  CAS  Google Scholar 

  3. Ye HM, Ren N, Zhang JJ, Sun SJ, Wang JF. Crystal structures, luminescent and thermal properties of a new series of lanthanide complexes with 4-ethylbenzoic acid. New J Chem, 2010, 34: 533–540

    Article  CAS  Google Scholar 

  4. Li X, Li YQ, Wu XS. 1-D and 2-D lanthanide coordination polymers constructed from 4-sulfobenzoate and 1,10-phenanthroline. Inorg Chem commum, 2008, 11: 774–778

    Article  CAS  Google Scholar 

  5. Bettencourt-Das AD. Isophthalato-based 2D coordination polymers of Eu(III), Gd(III), and Tb(III): Enhancement of the terbium-centered luminescence through thiophene derivatization. Inorg Chem, 2005, 44(8): 2734–2741

    Article  Google Scholar 

  6. Wan YH, Jin LP, Wang KZ, Zhang LP, Zheng XJ, Lu SZ. Hydrothermal synthesis and structural studies of novel 2-D lanthanide coordination polymers with phthalic acid. New J Chem, 2002, 26(11): 1590–1596

    Article  CAS  Google Scholar 

  7. Wang CG, Xing YH, Li ZP, Li J, Zeng XQ, Ge MF, Niu SY. A series of three-dimensional lanthanide-rigid-flexible frameworks: Synthesis, structure, and luminescent properties of coordination polymers with 2,5-pyridine dicarboxylic acid and adipic acid. Crys Growth De, 2009, 9(3): 1525–1530

    Article  CAS  Google Scholar 

  8. Huang CH. Coordination Chemistry of Rare Earths. Bingjing: Science Press, 1997. 378

    Google Scholar 

  9. Gao C, Cui K, She JB, Hou CQ, Guo HY, Zhao W, Wei W, Peng B. Optical properties of a novel neodymium pentafluoropropionate binuclear complex. Inorg Chim Acta, 2009, 362: 2001–2005

    Article  CAS  Google Scholar 

  10. Yang SP, Yang H, Yu XB, Wang ZM. Synthesis, structure and fluorescence of Eu2(NAP)6(PHEN)2 (NAPH = α-naphthoic acid; PHEN = 1,10-phenanthroline). J Mol Struct, 2003, 659: 97–102

    Article  CAS  Google Scholar 

  11. Yan B, Zhang HJ, Wang SB, Ni, JZ. Intramolecular energy transfer mechanism between ligands in ternary rare earth complexes with aromatic carboxylic acids and 1,10-phenanthroline. J photochem photobiol A: Chem, 1998, 116: 209–214

    Article  CAS  Google Scholar 

  12. Zolin V, Puntus L, Kudryashova V, Tsaryuk V, Legendziewicz J, Gawryszewska P, Szostak R. Charge transfer bands in the luminescence excitation spectra of isomeric pyridinedicarboxylic salts of europium. J Alloys Compd, 2002, 341: 376–380

    Article  CAS  Google Scholar 

  13. Bakhtiar R, Ochiai EI. Pharmacological applications of inorganic complexes. Gen Pharmacol, 1999, 32: 525–540

    Article  CAS  Google Scholar 

  14. He QZ, Yang J, Min H, Li HX. Studies on the spectra and antibacterial properties of rare earth dinuclear complexes with L-phenylala-nine and o-phenanthroline. Mater Lett, 2006, 60: 317–320

    Article  CAS  Google Scholar 

  15. Premkumar T, Govindarajan S. Antimicrobial study on trivalent lighter rare-earth complexes of 2-pyrazinecarboxylate with hydrazinium cation. World J Microbiol Biotechnol, 2006, 22: 1105–1108

    Article  CAS  Google Scholar 

  16. Breen C, Last PM, Taylor S, Komadel P. Synergic chemical analysis — The coupling of TG with FTIR, MS and GC-MS 2. Catalytic transformation of the gases evolved during the thermal decomposition of HDPE using acid-activated clays. Thermochim Acta, 2000, 363: 93–104

    Article  CAS  Google Scholar 

  17. Xie W, Pan WP. Thermal characterization of materials using evolved gas analysis. J Therm Ana Cal, 2001, 65: 669–685

    Article  CAS  Google Scholar 

  18. Li J, Liu YW, Shi JY, Wang ZY, Hu L, Yang X, Wang CX. The investigation of thermal decomposition pathways of phenylalanine and tyrosine by TG-FTIR. Thermochim Acta, 2008, 467: 20–29

    Article  CAS  Google Scholar 

  19. Sheldrick GM. SHELXS 97, Program for the Solution of Crystal Structure. Germany: University of Gottingen. 1997

    Google Scholar 

  20. Sheldrick GM. SHELXL 97, Program for the Refinement of Crystal Structure. Germany: University of Gottingen. 1997

    Google Scholar 

  21. Shi YZ, Sun XZ, Jiang YH. Spectra and Chemical Identification of Organic Compounds. Nanjing: Science and Technology Press, 1988. 98

    Google Scholar 

  22. Bai GB, Chen GD, Wang ZM, Yuan L, Kang ZW, Gao JZ. Synthesis and characterization of Ln(III)-Glycine-1,10-phenathroline ternary chelates. Chin J Inorg Chem, 1988, 4(2): 32–41

    CAS  Google Scholar 

  23. An BL, Gong ML, Li MX, Zhang JM. Synthesis, structure and luminescence properties of samarium(III) and dysprosium(III) complexes with a new tridentate organic ligand. J Mol Struct, 2004, 687: 1–6

    Article  CAS  Google Scholar 

  24. Wang LF, Wu JG, Peng ZR, Ran W, Yan GH. Study on ternary complexes of rare earth elements. IV. Syntheses and properties of ternary complexes of rare earth elements with 3,5-dinitrosalicylic acid and phenanthroline. Chin J Inorg Chem, 1990, 6: 141–146

    Google Scholar 

  25. Li X, Jin LP, Wan YH. Crystal structure and luminescence of a europium coordination polymer {[Eu(p-MOBA)3·2H(2)O]·0.5H2O 0.5(4,4′-bipy)}. Chin J Chem, 2002, 20: 352–357

    Article  CAS  Google Scholar 

  26. Yin MC, Ai CC, Yuan LJ, Wang CW, Sun JT. Synthesis, structure and luminescent property of a binuclear terbium complex [Tb2(Hsal)8(H2O)2][(Hphen)2]·2H2O. J Mol Struct, 2004, 691: 33–37

    Article  CAS  Google Scholar 

  27. Wang JF, Ren N, Zhang JJ, Wu KZ, Wang SP. Synthesis, crystal structure, and thermal properties of a holmium(III) benzoate complex with 1,10-phenanthroline. J Chem Eng Data, 2010, 55: 4982–4989

    Article  CAS  Google Scholar 

  28. Vyazovkin S, Dollimore D. Linear and nonlinear procedures in isoconversional computations of the activation energy of nonisothermal reactions in solids. J Chem Inf Comput Sci, 1996, 36: 42–45

    Article  CAS  Google Scholar 

  29. Vyazovkin S. Kinetic concepts of thermally stimulated reactions in solids: A view from a historical perspective. Int Rev Phys chem, 2000, 19: 45–60

    Article  CAS  Google Scholar 

  30. Vyazovkin S, Wight CA. Model-free and model-fitting approaches to kinetic analysis of isothermal and nonisothermal data. Thermochim Acta, 1999, 340–341: 53–68

    Article  Google Scholar 

  31. Lu ZR, Ding YC, Xu Y, Chen SH, Yu YP. Thermal behavior and decomposition kinetics. J Therm Anal Cal, 2003, 73: 333–340

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Experimental Center, Hebei Normal University, Shijiazhuang, 050016, China

    JuanFen Wang, JianJun Zhang & KeZhong Wu

  2. Shijiazhuang College, Shijiazhuang, 050035, China

    Hua Li

  3. Department of Chemistry, Handan College, Handan, 056005, China

    Ning Ren

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  1. JuanFen Wang
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  2. Hua Li
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  3. JianJun Zhang
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  4. Ning Ren
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Correspondence to JianJun Zhang.

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Wang, J., Li, H., Zhang, J. et al. Crystal structures and thermal decomposition mechanism of four lanthanide complexes with halogen-benzoic acid and 1,10-phenanthroline. Sci. China Chem. 55, 2161–2175 (2012). https://doi.org/10.1007/s11426-012-4595-9

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  • DOI: https://doi.org/10.1007/s11426-012-4595-9

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