Skip to main content
SpringerLink
Log in

Solid-state thermal degradation behaviour of 1-D coordination polymers of Ni(II) and Cu(II) bridged by conjugated ligand

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

Monometallic complexes [Cudadb·yH2O]n (2) and [Nidadb·yH2O]n (3) and heterobimetallic complex [Cu0.5Ni0.5dadb·yH2O]n (4) {where dadbH2 = 2,5-Diamino-3,6-dichloro-1,4-benzoquinone (1); y = 2–4; n = degree of polymerization} were characterized by elemental analysis, atomic absorption spectroscopy, infrared spectroscopy (FTIR) and powder X-ray diffraction. The thermal behaviour of the complexes was studied by thermal analysis (TG/DTA) under air as well as under helium atmospheres. The released gaseous products were investigated by evolved gas analysis performed by an online coupled mass spectrometer (TG/DTA-MS). Thermal degradation of 2 under helium atmosphere is distributed over five steps, whereas 3 and 4 exhibited only four degradation steps due to overlap of second and third degradation steps of into one major step. All the complexes exhibit three steps degradation under air. The complex 2 loses NH group in the second and HCl/Cl2, CO groups simultaneously in third steps of decomposition under helium, whereas it loses NH and CO groups simultaneously in low temperature region of second step of degradation under air atmosphere as the loss of CO group is facilitated by air. EGA-MS under air and helium atmospheres shows that HCl, CO/CO2 and (CN)2 fragments are lost simultaneously at multiple steps, and not successively as predicted earlier. Rate of evolution of most evolved gases exhibits several maxima as a consequence of degradation followed by recombination reactions. Final residues under air and helium atmospheres correspond to the metal oxides and metals along with some carbonaceous matter.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Condorelli GG, Malandrino G, Fragala I. Metal-organic chemical vapor deposition of copper and copper(I) oxide: kinetics and reaction mechanisms in the presence of oxygen. Chem Mater. 1995;7:2096–103.

    Article  CAS  Google Scholar 

  2. Poizot P, Laruelle S, Grugeon S, Dupont L, Taracon JM. Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature. 2000;407:496–9.

    Article  CAS  Google Scholar 

  3. MacDonald AH. A technique for injecting electrons into the surface layers of materials has now been applied to the most mysterious of superconducting compounds—the copper oxides. Nature. 2001;414:409–10.

    Article  CAS  Google Scholar 

  4. Kumar RV, Diamant Y, Gedanken A. Sono chemical synthesis and characterization of nanometer-size transition metal oxides from metal acetates. Chem Mater. 2000;12(8):2301–5.

    Article  CAS  Google Scholar 

  5. Gao XP, Bao JL, Pan GL, Zhu HY, Huang PX, Wu F, Song DY. Preparation and electrochemical performance of polycrystalline and single crystalline CuO nanorods as anode materials for Li ion battery. J Phys Chem B. 2004;108:5547–51.

    Article  CAS  Google Scholar 

  6. Maruyama T. Copper oxide thin films prepared by chemical vapor deposition from copper dipivaloylmethanate. Sol Energy Mater Sol Cells. 1998;56:85–92.

    Article  CAS  Google Scholar 

  7. Ramirez-Ortiz J, Ogura T, Medina-Valtierra J, Acosta-Ortiz SE, Bosch P, De Los Reyes JA, Lara VH. A catalytic application of Cu2O and CuO films deposited over fiberglass. Appl Surf Sci. 2001;174:177–84.

    Article  CAS  Google Scholar 

  8. Allmendinger T. Synthesis and characterization of metal containing polychloranilamides. Macromol Chem Phys. 1997;198:4019–34.

    Article  CAS  Google Scholar 

  9. Prasad RL, Kushwaha A, Singh D. Synthesis, characterization and thermal degradation of 1-D coordination polymers of the type CuxZn1−x(dadb)·yH2O(dadb = 2,5-diamino-3,6-dichloro-1,4-benzoquinone; and x = 1.0, 0.5, 0.0625 and 0). Thermochim Acta. 2010;511:17–26.

    Article  CAS  Google Scholar 

  10. Prasad RL, Kushwaha A, Suchita, Kumar M, Yadav RA. Infrared and ab initio studies of conducting molecules: 2,5-diamino-3,6-dichloro-1,4-benzoquinone. Spectrochim Acta. 2008;A69:304–11.

  11. Creutz C, Taube H. Binuclear complexes of ruthenium ammines. J Am Chem Soc. 1973;95:1086–94.

    Article  CAS  Google Scholar 

  12. Cao M, Hu C, Wang Y, Guo Y, Guoa C, Wanga E. A controllable synthetic route to Cu, Cu2O, and CuO nanotubes and nanorods. Chem. Commun. 2003; 1884–85.

  13. Furmiss BS, Hannaford AJ, Rogers B, Smith PWG, Tatchell AR. Vogel’s text book of practical organic chemistry. 4th ed. London: ELBS; 1978.

  14. Fieser LF, Martin EL. A comparison of heterocyclic systems with benzene.VII. Isologs of anthraquinone containing one and two triazole rings. J Am Chem Soc. 1935;57:1844.

    Article  CAS  Google Scholar 

  15. Matsunaga Y, McDowell CA. The electron spins resonance absorption spectra of semiquinone ions, part II. The hyperfine splitting due to amino groups. Can J Chem. 1960;38:1167–71.

    Article  Google Scholar 

  16. Prasad RL, Kushwaha A, Shrivastava ON. Synthesis, characterization and solid state electrical properties of 1-D coordination polymer of the type [CuxNi1−x(dadb)yH2O]n. J Solid State Chem. 2012;196:471–81.

    Article  CAS  Google Scholar 

  17. D’Souza L, Devi P, Shridhar MPD, Naik CG. Use of Fourier transform infrared (FTIR) spectroscopy to study cadmium-induced changes in Padina Tetrastromatica (Hauck). Anal Chem Insights. 2008;3:135–43.

    Google Scholar 

  18. Kuramshin AI, Kuramshina EA, Cherkasov RA. Synthesis of mesityl oxide p-complexes with metals of chromium subgroup and with iron. Theoretical and experimental investigation of the ligand dissociation energy. Russ J Org Chem. 2005;41:649–55.

    Article  CAS  Google Scholar 

  19. Kawata S, Kitagawa S, Furuchi I, Kudo C, Kamesaki H, Kondo M, Katada M, Munakata M. Synthesis, structure, and magnetic properties of crystalline coordination polymers of copper(II),{[Cu(CA)(H2O)2(H2O)}n and [Cu(CA)(MeOH)2n (H2CA; chloranilic acid)]. Mol Cryst Liq Cryst. 1995;274:179–85.

    Article  Google Scholar 

  20. Azaroff LV, Buerger MJ. The powder method in X-ray crystallography. New York: McGraw-Hill; 1958. p. 119.

    Google Scholar 

  21. Sallam SA. Binuclear copper(II), nickel(II) and cobalt(II) complexes with N2O2 chromophores of glycylcine Schiff-bases of acetylacetone, benzoylacetone and thenoyltrifluroacetone. Transition Met Chem. 2006;31:46–55.

    Article  CAS  Google Scholar 

  22. Madarász J, Szilágyi IM, Hange F, Pokol G. Comparative evolved gas analyses (TG-FTIR, TG/DTA-MS) and solid state (FTIR, XRD) studies on thermal decomposition of ammonium paratungstate tetrahydrate (APT) in air. J Anal Appl Pyrolysis. 2004;72:197–201.

    Article  Google Scholar 

  23. Szilagyi IM, Madarasz J, Pokol G, Kiraly P, Tarkanyi G, Saukko S, Mizsei J, Toth AL, Szabo A, Varga-Josepovits K. Stability and controlled composition of hexagonal WO3. Chem Mater. 2008;20:4116–25.

    Article  CAS  Google Scholar 

  24. Akama Y. Thermal decomposition of copper complexes of 1–phenyl–3–methyl-4–acyl–5–pyrazolone in air atmosphere. J Therm Anal. 1995;45:1501–6.

    Article  CAS  Google Scholar 

  25. Abdalla EM, Said AA. Thermal studies on cobalt(II), nickel(II) and copper(II) ternary complexes of N-(2-acetamido)iminodiacetic acid and imidazoles. Thermochim Acta. 2003;405:269–77.

    Article  CAS  Google Scholar 

  26. Verma RK, Verma L, Chandra M, Bhushan A. Non-isothermal dehydration and decomposition of dl-lactates of transition metals and alkaline earth metals. A comparative study. J Therm Anal Calorim 2005;80:351–4.

    Article  CAS  Google Scholar 

  27. Yang Z, Xu J, Zhang W, Liu A, Tang S. Controlled synthesis of CuO nanostructures by a simple solution route. J Solid State Chem. 2007;180:1390–6.

    Article  CAS  Google Scholar 

  28. Roman P, Guzmam-Miralles C, Luque A, Seco ML. Studies on the thermal decomposition of dipotassium trans-diaquabis(oxalato-O, O’)nickelate(II) tetrahydrate. Thermochim Acta. 1995;257:67–73.

    Article  CAS  Google Scholar 

  29. Lay E, Song Y-H, Chiu Y-C, Lin Y-M, Chi Y. New CVD precursors capable of depositing copper metal under mixed O2/Ar atmosphere. Inorg Chem. 2005;44:7226–33.

    Article  CAS  Google Scholar 

  30. Akanni MS, Ajayi OB, Lanbi JN. Pyrolytic decomposition of some even chain length copper(II) carboxylates. J Therm Anal Calorim. 1986;31:131–43.

    Article  CAS  Google Scholar 

  31. Krunks M, Leskela T, Mannonen R, Niinisto L. Thermal decomposition of copper(I) thiocarbamide chloride hemihydrates. J Therm Anal Calorim. 1998;53:541–4.

    Article  Google Scholar 

Download references

Acknowledgements

Authors are thankful to the Head, Department of Chemistry, for providing laboratory facilities, recording of IR and DSC curves. Financial assistant from UGC New Delhi in form of a project is gratefully acknowledged. Prof. R. K. Mandal, department of Metallurgy, IT, BHU, is gratefully acknowledged for recording PXRD of metal complexes. Thanks are also due to SAIF, Cochin, for providing TG, DTG and DTA curves under air atmosphere at PED thermal analyzer. Imre M. Szilágyi thanks for a János Bolyai Research Fellowship of the Hungarian Academy of Sciences.

Author information

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi, 221005, India

    Ram Lakhan Prasad, Anita Kushwaha & Rajesh Kumar

  2. Research Group of Technical Analytical Chemistry of the Hungarian Academy of Sciences, Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szt. Gellért tér 4, Budapest, 1111, Hungary

    Imre Miklós Szilágyi

  3. Research Centre for Natural Sciences, Hungarian Academy of Sciences, Pusztaszeri u. 59-67, Budapest, 1025, Hungary

    László Kótai

Authors
  1. Ram Lakhan Prasad
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Anita Kushwaha
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Rajesh Kumar
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Imre Miklós Szilágyi
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. László Kótai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ram Lakhan Prasad.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (PDF 504 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Prasad, R.L., Kushwaha, A., Kumar, R. et al. Solid-state thermal degradation behaviour of 1-D coordination polymers of Ni(II) and Cu(II) bridged by conjugated ligand. J Therm Anal Calorim 114, 653–664 (2013). https://doi.org/10.1007/s10973-013-2983-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-013-2983-9

Keywords

Search

Navigation