Journal of Thermal Analysis and Calorimetry

, Volume 103, Issue 2, pp 525–531 | Cite as

Luminescence and thermal behavior by simultaneous TG/DTG–DTA coupled with MS of neutral copper (I) complexes with heterocyclic thiones

  • P. Aslanidis
  • V. Gaki
  • K. Chrissafis
  • M. Lalia-Kantouri


Copper(I) halide complexes formulated as [(L)CuX(μ2-L)2CuX(L)] (X = Cl, Br and L = pyridine-2-thione (py2SH), or 4,6-dimethylpyrimidine-2-thione (dmpymtH)) were prepared, and their photoluminescence and thermal properties were investigated. The complexes are strongly emissive in the solid state, with the emissions being dominated by large Stokes shifts (>200 nm), which are depending on both the heterocyclic thione and the nature of the halogen. These emissions can be assigned to MLCT with some mixing of the halide-to-ligand (XL) CT characters. Simultaneous TG/DTG–DTA technique, coupled with MS for the analysis of the gaseous decomposition products, was used for two complexes with the dmpymtH ligand to determine their thermal degradation, which was found to be very complicated. In inert atmosphere the residues at 1,000 °C (verified with PXRD) were a mixture of Cu2S and CuX, while at 1,300 °C a mixture of Cu2S and Cu. In oxygen atmosphere the residues were CuO.


Copper(I) complexes Heterocyclic thiones Luminescence TG/DTG–DTA Coupled TG–MS PXRD 

Supplementary material

10973_2010_974_MOESM1_ESM.jpg (634 kb)
Supplementary material 1 (JPEG 633 kb) PXRD of the complex [CuCl(py2SH)2]2
10973_2010_974_MOESM2_ESM.jpg (649 kb)
Supplementary material 2 (JPEG 648 kb) PXRD of the complex [CuBr(py2SH)2]2
10973_2010_974_MOESM3_ESM.jpg (641 kb)
Supplementary material 3 (JPEG 641 kb) PXRD of the complex [CuCl(dmpymtH)2]2
10973_2010_974_MOESM4_ESM.jpg (670 kb)
Supplementary material 4 (JPEG 670 kb) PXRD of the complex [CuBr(dmpymtH)2]2


  1. 1.
    Krebs B, Henkel G. Transition-metal thiolates: from molecular fragments of sulfidic solids to models for active centers in biomolecules. Angew Chem Int Ed. 1991;30:769–88.CrossRefGoogle Scholar
  2. 2.
    Holm RH, Solomon EJ. Structural and functional aspects of metal sites in biology. Chem Rev. 1996;96:2239–314.CrossRefGoogle Scholar
  3. 3.
    Raper ES. Complexes of heterocyclic thione donors. Coord Chem Rev. 1985;61:115–84.CrossRefGoogle Scholar
  4. 4.
    Raper ES. Complexes of heterocyclic thioamides and related ligands. Coord Chem Rev. 1994;129:91–156.CrossRefGoogle Scholar
  5. 5.
    Raper ES. Complexes of heterocyclic thionates. Part 1. Complexes of monodentate and chelating ligands. Coord Chem Rev. 1996;153:199–255.CrossRefGoogle Scholar
  6. 6.
    Mentzafos D, Terzis A, Karagiannidis P, Aslanidis P. Structure of bis(μ-pyridine-2-thione-μ- S)-bis[iodo(pyridine-2-thione-S)copper(I)]. Acta Crystallogr. 1989;C45:54–6.Google Scholar
  7. 7.
    Aslanidis P, Cox PJ, Divanidis S, Karagiannidis P. Copper(I) halide complexes from cis-1, 2-bis(diphenylphosphino)ethylene and some heterocyclic thiones. Inorg Chim Acta. 2004;357:1063–76.CrossRefGoogle Scholar
  8. 8.
    Aslanidis P, Hadjikakou SK, Karagiannidis P, Kojic-Prodic B, Luic M. Preparation and spectral studies of dinuclear mixed-ligand copper(I) complexes. The crystal structure of bis[μ-S(pyridine-2-thione)(tmtp)copper(I) bromide]. Polyhedron. 1994;13:3119–25.CrossRefGoogle Scholar
  9. 9.
    Aslanidis P, Cox PJ, Divanidis S, Tsipis AC. Copper(I) halide complexes with 1,3-propanebis(diphenylphosphine) and heterocyclic thione ligands: crystal and electronic structures (DFT) of [CuCl(pymtH)(dppp)], [CuBr(dppp)], [Cu(μ-I)(dppp)]2. Inorg Chem. 2002;41:6875–86.CrossRefGoogle Scholar
  10. 10.
    Li D, Shi W-J, Hou L. Coordination polymers of copper(I) halides and neutral heterocyclic thiones with new coordination modes. Inorg Chem. 2005;44:3907–13.CrossRefGoogle Scholar
  11. 11.
    Mandal TN, Roy SN, Barik AK, Gupta S, Butcher RJ, Kar SK. Unusual complexation of Cu(II) by pyrimidine/pyridine-pyrazole derived ligands exploiting the molecular function of 2-mercapto-4,6-dimethylpyrimidine. Synthesis, crystal structures and electrochemistry. Inorg Chim Acta. 2009;362:1315–22.CrossRefGoogle Scholar
  12. 12.
    Scaltrino DV, Thompson DW, O’Callaghan JA, Meyer GJ. MLCT excited states of cuprous bis-phenanthroline coordination compounds. Coord Chem Rev. 2000;208:243–66.CrossRefGoogle Scholar
  13. 13.
    Mc Millin DR, McNett KM. Photoprocesses of copper complexes that bind to DNA. Chem Rev. 1998;98:1201–20.CrossRefGoogle Scholar
  14. 14.
    Armaroli N. Photoactive mono- and polynuclear Cu(I)-phenanthrolines. A viable alternative to Ru(II)-polypyridines? Chem Soc Rev. 2001;30:113–24.CrossRefGoogle Scholar
  15. 15.
    Hadjikakou SK, Aslanidis P, Akrivos PD, Karagiannidis P, Kojic-Prodic B, Luic M. Study of mixed ligand copper(I) complexes with tri-m-tolylphosphine (tmpt) and heterocyclic thiones. Crystal structures of bis[μ-S(benzimidazoline-2-thione)(tmpt)copper(I) chloride] and bis[μ-Br(thiazolidine-2-thione)(tmpt)copper(I)]. Inorg Chim Acta. 1992;197:31–3.CrossRefGoogle Scholar
  16. 16.
    Falcomer VAS, Lemos SS, Batista AA, Ellena J, Castellano EE. Mono- and dinuclear copper(I) complexes with methyl substituted pyrimidinethiones. Inorg Chim Acta. 2006;359:1064–70.CrossRefGoogle Scholar
  17. 17.
    Pawlowsky V, Knör G, Lennartz C, Vogler A. Luminescence and theoretical studies of Cu(tripod)X [tripod = 1,1,1-tris(diphenylphosphanylmethyl)ethane; X = halide, thiophenolate, phenylacetylide]. Eur J Inorg Chem. 2005;15:3167–71.CrossRefGoogle Scholar
  18. 18.
    Araki H, Tsuge K, Sasaki Y, Ishizaka S, Kitamura N. Luminescence ranging from red to blue: a series of copper(I)–halide complexes having rhombic Cu2(μ − X)2 (X = Br and I) units with N-heteroaromatic ligands. Inorg Chem. 2005;44:9667–75.CrossRefGoogle Scholar
  19. 19.
    Rath NP, Holt EM, Tanimura K. Fluorescent copper(I) complexes: structural and spectroscopic characterization of bis(p-toluidine)bis(acetonitrile) tetraiodotetracopper and bis[p-chloroaniline)(acetonitrile)diiododicopper] tetrameric complexes of mixed-ligand character. Inorg Chem. 1985;24:3934–8.CrossRefGoogle Scholar
  20. 20.
    Aslanidis P, Cox PJ, Kapetangiannis K, Tsipis A. Structural and spectroscopic properties of new copper(I) complexes with 1,1,1-tris(diphenylphosphanylmethyl)ethane and heterocyclic thiolates. Eur J Inorg Chem. 2008;32:5029–37.CrossRefGoogle Scholar
  21. 21.
    Goher MAS, Mak TCW. Three coordinate copper(I) complexes. Synthesis, spectral and structural study of copper(I) complexes of 4-benzoylpyridine and X-ray crystal structure of the dimer [CuCl(4-benzoylpyridine)]2. Polyhedron. 1998;17:3485–94.CrossRefGoogle Scholar
  22. 22.
    Lazarou K, Bednarz B, Kubicki M, Vergiadis I, Charalabopoulos K, kourkoumelis N, Hadjikakou SK. Structural, photolysis and biological studies of the bis(μ-chloro)-tris(triphenylphosphine)–di-copper(I) and chloro-tris(triphenylphosphine)–copper(I) complexes. Study of copper(I)–copper(I) interactions. Inorg Chim Acta. 2010;363:763–72.CrossRefGoogle Scholar
  23. 23.
    Krunks M, Leskela T, Mutikainen I, Niinisto LA. Thermoanalytical study of copper (I) thiocarbamate compounds. J Therm Anal Calorim. 1999;56:479–84.CrossRefGoogle Scholar
  24. 24.
    Krunks M, Leskela T, Mannomen R, Niinisto LA. Thermal decomposition of copper(I) thiocarbamate hemihydrate. J Therm Anal Calorim. 1998;53:355–64.CrossRefGoogle Scholar
  25. 25.
    Madarasz J. Evolved gas analyses on mixed valence copper (I, II) complex salt with thiosulfate and ammonia by in situ TG-EGA-FTIR and TG/DTA-EGA-MS. J Therm Anal Calorim. 2009;97:111–6.CrossRefGoogle Scholar
  26. 26.
    Powder Diffraction Files, JCPDS-ICDD, 2005; 20:PDF files for Cu–S, Cu–Br and Cu–O phases in legends of Fig. 4 and Fig. 7.Google Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2010

Authors and Affiliations

  • P. Aslanidis
    • 1
  • V. Gaki
    • 1
  • K. Chrissafis
    • 2
  • M. Lalia-Kantouri
    • 1
  1. 1.Laboratory of Inorganic Chemistry, Department of Chemistry, Faculty of SciencesAristotle University of ThessalonikiThessalonikiGreece
  2. 2.Solid State Physics Department, School of PhysicsAristotle University of ThessalonikiThessalonikiGreece

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