View More View Less
  • 1 Institute of General and Ecological Chemistry, Technical University of Lodz, Lodz, Poland
Restricted access

Abstract

Novel mixed-ligand complexes with empirical formula Ln(4-bpy)2(CCl3COO)3·nH2O [where Ln(III) = Dy, Ho, Er, Tm, Yb, Lu; 4-bpy = 4,4′-bipyridine] were prepared and characterized by chemical and elemental analysis, infrared spectroscopy, and conductivity measurements (in methanol, dimethylformamide, and dimethyl sulfoxide). X-ray powder diffraction patterns indicate that the complexes are small crystalline compounds. IR spectra of complexes show that all carboxylate groups and 4-bpy are engaged in coordination of lanthanide ions. The thermal behavior of complexes was studied by means of TG, DTG, DTA techniques in the solid state under nonisothermal conditions in air atmosphere. During heating, the complexes decompose via intermediate products to the oxide Ln2O3. The combined TG–FTIR technique was employed to study the decomposition pathway of the Ho(III) and Tm(III) complexes in flowing argon atmosphere.

  • 1.

    Blower, PJ. 2000. Inorganic pharmaceuticals. Annu Rep Prog Chem A. 96:645662 .

  • 2.

    Łyszczek, R. 2010. Synthesis, structure, thermal and luminescent behavior of lanthanide-pyridine_3, 5-dicarboxylate frameworks series. Thermochim Acta. 509:120127 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 3.

    Woods, M, Kavacs, Z, Sherry, AD. 2002. Targeted complexes of lanthanide(III) ions as therapeutic and diagnostic pharmaceuticals. J. Supramol. Chem. 2:115 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 4.

    Chang, WB, Zhang, BL, Li, LZ, Ci, YX. 1997. Double-label simultaneous time-resolved fluoroimmunoassay of phenytoin and phenobarbital. Microchem J. 55:287295 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5.

    Ferri, D, Forni, L. 1998. Methane combustion on some perovskite-like mixed oxides. Appl Catal B Environ. 16:119126 .

  • 6.

    Parac-Vogt, TN, Binnemans, K. 2004. Lanthanide(III) nosylates as new nitration catalysts. Tetrahedron Lett. 45:31373139 .

  • 7.

    Batten, A, Robson, R. 1998. Interpenetrating nets: ordered, periodic entanglement. Angew Chem Int Ed. 37:14611494 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8.

    Janiak, C. 1997. Functional organic analogues of zeolites based on metal–organic coordination frameworks. Angew Chem Int Ed Engl. 36:14311434 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9.

    Tao J , Tong ML, Chen XM (2000) Hydrothermal synthesis and crystal structures of three-dimensional co-ordination frameworks constructed with mixed terephthalate (tp) and 4,4′-bipyridine (4,4′-bipy) ligands: [M(tp)(4,4′-bipy)] (M = CoII, CdII or ZnII). J Chem Soc Dalton Trans. 366974.

    • Search Google Scholar
    • Export Citation
  • 10.

    Zaworotko, MJ. 2001. Superstructural diversity in two dimensions: crystal engineering of laminated solids. Chem Commun. 1:19 .

  • 11.

    Czylkowska, A, Kruszyński, R, Czakis-Sulikowska, D, Markiewicz, M. 2007. Coordination polymer of lanthanum: synthesis, properties and crystal structure of [La(4,4′-bipyridine)(CCl2HCOO)3(H2O)]n. J Coord Chem. 60:26592669 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12.

    Sain, S, Maji, TK, Mostafa, G, Lu, TH, Chudhuri, VR. 2003. Two new supramolecular malonato complexes of manganese(II): synthesis, crystal structure and magnetic property. Inorg Chim Acta. 351:1220 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13.

    Li, JM, Zhang, YG, Chen, JH, Wang, QM, Wu, XT. 2000. Microporous networks co-assembled by both rigid and flexible building blocks. Polyhedron. 19:11171121 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 14.

    Tao, I, Yin, X, Huang, R, Zhang, L. 2001. Hydrothermal synthesis of a novel microporous framework sustained by polycatenated [CuI2(ip)(4,4′-bipyridine)]n (ip = isophthalate) ladders. Inorg Chem Commun. 5:10001002 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 15.

    Carballo, R, Castiňeiras, A, Covelo, B, Váquez-Lopez, EM. 2001. Coordination polymers of copper(II) based on mixed N- and O-donor ligands: the crystal structures of [CuL2(4,4′-bipy)]n (L = lactate or 2-methyllactate). Polyhedron. 20:899904 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 16.

    Oczko, G, Starynowicz, P. 2005. Comparison of optical properties and crystal structures of the praseodymium and europium chloroderivatives of acetates. J Mol Struct. 740:237248 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17.

    Oczko, G, Legendziewicz, J, Mroziński, J, Meyer, G. 1998. Comparative spectroscopic and magnetic studies of two types of Ln and Ln:Cu trichloroacetates. J Alloys Compd. 219:275277.

    • Search Google Scholar
    • Export Citation
  • 18.

    Legendziewicz, J, Borzechowska, M, Oczko, G, Mroziński, J. 1998. Polymeric polynuclear systems of Pr, Yb and Pr:Cu trichloroacetates; their spectroscopy and magnetism. Spectrochim Acta A. 54:21972205 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19.

    Voronkova VK , Galeev RT, Legendziewicz J, Oczko G (2000) EPR spectra of alternating chains in (Nd2(CCl3COO)6(H2O)3]n·nH2O. XIIth Winter School on Coordination Chemistry, Karpacz, 4-8 Dec, p. 89.

    • Search Google Scholar
    • Export Citation
  • 20.

    Voronkova VK , Yablokov V, Oczko G Polynuclear complexes of lanthanides with trichloroacetate ligands: syntheses, structures and EPR studies of Nd(CCl3COO)3·2H2O (Nd, Cu)(CCl3COO)8·6H2O and (Nd, La)(CCl3COO)3·2H2O. XIIIth Summer School on Coordination Chemistry, Polanica Zdrój, 2-8 June 1996, p. 177.

    • Search Google Scholar
    • Export Citation
  • 21.

    Barja, B, Baggio, R, Garland, MT, Aramendio, PF, Pena, O, Perec, M. 2003. Crystal structures and luminescent properties of terbium(III) carboxylates. Inorg Chim Acta. 346:187196 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 22.

    Łyszczek, R. 2007. Thermal and spectroscopic investigations of new lanthanide complexes with 1,2,4-benzenetricarboxylic acid. J Therm Anal Calorim. 90:533539 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 23.

    Łyszczek, R. 2008. Comparison of thermal properties of lanthanide trimellitates prepared by different methods. J Therm Anal Calorim. 93:833838 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24.

    Imai, T, Shimoi, M, Ouchi, Z. 1987. The crystal and molecular structure of the hydrated light lanthanoid(III) chloroacetates, [{M(ClCH2CO2)3}3(H2O)5]n (M = La, Pr, Nd and Eu). Bull Chem Soc Jpn. 60:159169 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 25.

    Rohde A , Urland W (2006) Catena-poly[[(2,2′-bipyridine-j2 N,N′)-neodymium(III)]-l-dichloroacetato-1j2O:O′:2jOdi-l-dichloroacetato-j4O:O″]. Acta Crystallogr Sec E. 2006; 62(7):m1618-m1619. doi: .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26.

    Rohde A , Urland W (2006) Catena-poly[[(2,2″-bipyridine-j2 N,N″)-praseodymium(III)]-l-dichloroacetate-1j2O:O″:2jO-di-l-dichloroacetato-j4O:O″]. Acta Crystallogr E. 2006; 62(11):m2843-m2845. doi: .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27.

    John, D, Urland, W. 2006. Synthesis, crystal structure, and magnetic behaviour of [Gd2(ClF2CCOO)6(H2O)2(bipy)2]2·C2H5OH. Z Anorg Allg Chem. 632 10 17681770 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 28.

    John, D, Urland, W. 2005. Crystal structure and magnetic behaviour of the new gadolinium complex compound Gd2(ClH2CCOO)6(bipy)2. Eur J Inorg Chem. 22:44864489 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 29.

    Rohde, A, John, D, Urland, W. 2005. Crystal structures of Gd2(Cl3CCOO)6(bipy)2(H2O)2·4-bipy, Pr(Cl3CCOO)3(bipy)2, Nd(Cl3CCOO)3(bipy)2 and Er(Cl3CCOO)3(bipy)2(H2O). Z Kristal. 220 2 177182 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 30.

    Spacu, F, Antonescu, E. 1969. Complexes of lanthanide haloacetates with 1,10-phenanthroline and 2,2′-bipyridine. Rev Roum Chim. 14:201207.

    • Search Google Scholar
    • Export Citation
  • 31.

    Hart, FA, Laming, J. 1965. Lanthanide complexes-III: complexes of 2,2′-dipyridyl with lanthanide chlorides, thiocyanates, acetates and nitrates. J Nucl Chem. 27:18251829 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 32.

    Kokonov, JV, Segal, EJ. 1971. Thermal decomposition of complexes of neodynium and erbium with 1,10-phenanthroline and 2,2′-bipyridyl. Rev Roum Chim. 16:16471650.

    • Search Google Scholar
    • Export Citation
  • 33.

    Czylkowska, A, Czakis-Sulikowska, D, Kaczmarek, A, Markiewicz, M. 2011. Thermal behavior and other properties of Pr(III), Sm(III), Eu(III), Gd(III), Tb(III) complexes with 4,4′-bipyridine and trichloroacetates. J Therm Anal Calorim. 105:331339 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 34.

    Czakis-Sulikowska, D, Czylkowska, A, Markiewicz, M. 2007. Synthesis, characterization and thermal decomposition of yttrium and light lanthanides with 4,4′-bipyridine and dichloroacetates. Pol J Chem. 81:12671275.

    • Search Google Scholar
    • Export Citation
  • 35.

    Kruszyński, R, Czylkowska, A, Czakis-Sulikowska, D. 2006. A novel carboxylic coordination polymer of samarium(III): [Sm(H2O)(4,4′-bipyridine)(CCl2HCOO)3]n. J Coord Chem. 59:681690 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 36.

    Czakis-Sulikowska, D, Czylkowska, A, Markiewicz, M, Frajtak, M. 2009. Synthesis and properties of complexes of Gd(III), Tb(III), Ho(III) and Tm(III) with 4,4′-bipyridine and dichloroacetates. Pol J Chem. 83:18931901.

    • Search Google Scholar
    • Export Citation
  • 37.

    Czylkowska, A, Markiewicz, M. 2010. Coordination behaviour and thermolysis of some rare-earth complexes with 4,4′-bipyridine and di- or trichloroacetates. J Therm Anal Calorim. 100:717723 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 38.

    Czylkowska, A, Czakis-Sulikowska, D, Kruszyński, R, Markiewicz, M. 2009. Synthesis, crystal structure and other properties of the complexes of Er(III), Yb(III) and Lu(III) with 4,4′-bipyridine and dichloroacetates. Struct Chem. 21:415423 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 39.

    Powder Diffraction File, PDF-2, release 2004. The International Centre for Diffraction Data (ICDD), Newton Square.

  • 40.

    Geary, WI. 1971. The use of conductivity measurements in organic solvents for the characterisation of coordination compounds. Coord Chem Rev. 7:81122 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 41.

    Pearce, CK, Grosse, DW, Hessel, W. 1970. Effect of molecular structure on infrared spectra of six isomers of bipyridine. Chem Eng Data. 15:567570 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 42.

    Ahuja, IS, Singh, R, Yadava, GL. 1981. Structural information on manganese(II) chloride, thiocyanate, acetate and sulphate complexes with 2,2′-bipyridyl, 4,4′-bipyridyl and their dioxides fr. J Mol Struct. 74:143151 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 43.

    Deacon, GB, Philips, RI. 1980. Relationships between the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination. Coord Chem Rev. 33:227250 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 44.

    Nakamoto, K. 2009 Infrared and Raman spectra of inorganic and coordination compounds Wiley New York.

  • 45.

    Manhas, BS, Trikha, AK. 1982. Relationships between the direction of shifts in the carbon-oxygen stretching frequencies of carboxylato complexes and the type of carboxylate coordination. Indian J Chem. 59:315319.

    • Search Google Scholar
    • Export Citation
  • 46.

    Brzyska, W, Ożga, W. 2006. Spectral, magnetic and thermal investigations of some d-electron element 3-methoxy-4-methylbenzoates. J Therm Anal Calorim. 84:385389 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 47.

    Zelenak, V, Vargova, Z, Gyoryova, K. 2007. Correlation of infrared spectra of zinc(II) carboxylates with their structures. Spectrochim Acta A. 66:262272 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 48.

    Brzyska, W, Dębska, E, Szczotka, M. 2001. New complexes of rare earth elements with methylsuccinic acid. Pol J Chem. 75:13931399.

  • 49.

    Schultze, D. 1974 Differential thermoanalyse VEB Deutscher Verlag der Wissenschaften Berlin.

  • 50.

    Liptay, G, Kenessey, G, Bihatsi, L, Wadsten, T, Mink, J. 1992. Pyridine type complexes of transition-metal-halides. Preparation, characterization and thermal analysis studies of cobalt(II)-chlorides with 2,3,4-methylpyridines. J Therm Anal Calorim. 38:899905 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 51.

    Zapata, B, Balmaseda, J, Fregoso-Israel, E, Torres-Garcia, E. 2009. Thermo-kinetics study of orange peel in air. J Therm Anal Calorim. 98:309315 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 52.

    Souza, BS, Moreira Ana Paula, D, Teixeira Ana Maria, RF. 2009. TG-FTIR coupling to monitor the pyrolysis products from agricultural residues. J Therm Anal Calorim. 97:637642 .

    • Crossref
    • Search Google Scholar
    • Export Citation