Skip to main content
SpringerLink
Log in

Structural and thermal characterization of copper(II) complexes with phenyl-2-pyridylketoxime and deposition of thin films by spin coating

  • Original Paper
  • Published:
Chemical Papers Aims and scope Submit manuscript

Abstract

Four copper(II) oxime complexes, [Cu(HPPK)(PPK)X] (HPPK = phenyl-2-pyridylketoxime and X = CI− (I), CF3COO− (II), C3F7COO− (III), and [Cu(PPK)2]2 (IV)), were synthesized and characterized by elemental analysis, infrared spectroscopy (IR), and single-crystal X-ray diffraction (XRD). XRD analysis revealed that I–III contain copper(II) coordinated by four nitrogen atoms from two oxime molecules in the basal plane and one monodentate anion X in the apical position of a distorted square pyramid. Complex IV is dimeric and it is formed by two Cu(PPK)2 units. Bridges between these units are formed by the two oxygen atoms of the deprotonated oxime groups. Thermal stability of I–IV was investigated by thermogravimetric analysis (TGA) in air and in nitrogen atmosphere, respectively. Evolved gaseous decomposition products were characterized by IR. I–IV decompose via multistep processes. Fluorocarbons and CO2 were observed to be the most abundant gaseous species evolved. Preliminary ammonolysis experiments were performed to examine the possibility of using II and IV as precursors for the synthesis of copper nitride. Moreover, solutions of IV were spin-coated onto silicon substrates. Surface structure and morphology of the resulting films were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM) and layers with island-like distribution of material were observed.

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

Similar content being viewed by others

References

  • Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J., & Verschoor, G. C. (1984). Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen-sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate. Journal of the Chemical Society, Dalton Transactions, 1984, 1349–1356. DOI: 10.1039/dt9840001349.

    Article  Google Scholar 

  • Afrati, T., Dendrinou-Samara, C., Raptopoulou, C., Terzis, A., Tangoulis, V., & Kessissoglou, D. P. (2007). Copper inverse-9-metallacrown-3 compounds showing antisymmetric magnetic behaviour. Dalton Transactions, 2007, 5156–5164. DOI: 10.1039/b708767e.

    Article  Google Scholar 

  • Afrati, T., Pantazaki, A. A., Dendrinou-Samara, C., Raptopoulou, C., Terzis, A., & Kessissoglou, D. P. (2010). Copper inverse-9-metallacrown-3 compounds interacting with DNA. Dalton Transactions, 39, 765–775. DOI: 10.1039/b914112j.

    Article  CAS  Google Scholar 

  • Ando, M., Kobayashi, T., Iijima, S., & Haruta, M. (2003). Optical CO sensitivity of Au-CuO composite film by use of the plasmon absorption change. Sensors and Actuators B: Chemical, 96, 589–595. DOI: 10.1016/s0925-4005(03)00645-2.

    Article  CAS  Google Scholar 

  • Baker, P. G. L., Sanderson, R. D., & Crouch, A. M. (2007). Sol-gel preparation and characterisation of mixed metal tin oxide thin films. Thin Solid Films, 515, 6691–6697. DOI: 10.1016/j.tsf.2007.01.042.

    Article  CAS  Google Scholar 

  • Barreca, D., Gasparotto, A., Maccato, C., Tondello, E., Lebedev, O. I., & Van Tendeloo, G. (2009). CVD of copper oxides from a α-diketonate diamine precursor: tailoring the nano-organization. Crystal Growth & Design, 9, 2470–2480. DOI: 10.1021/cg801378x.

    Article  CAS  Google Scholar 

  • Bayansal, F., Çetinkara, H. A., Kahraman, S., Çakmak, H. M., & Güder, H. S. (2012). Nano-structured CuO films prepared by simple solution methods: Plate-like, needle-like and network-like architectures. Ceramics International, 38, 1859–1866. DOI: 10.1016/j.ceramint.2011.10.011.

    Article  CAS  Google Scholar 

  • Brandenburg, K. (2001). Diamond, Release 2.1e [computer software]. Bonn, Germany: Crystal Impact.

    Google Scholar 

  • Bräuer, B., Zahn, D.R. T., Rüffer, T., & Salvan, G. (2006). Deposition of thin films of a transition metal complex by spin coating. Chemical Physics Letters, 432, 226–229. DOI: 10.1016/j.cplett.2006.10.070.

    Article  Google Scholar 

  • Bucci, R., Carunchio, V., Magri, A. D., & Magri, A. L. (1984). The thermal decomposition reactions of bis-(pyridine-2-aldoxime)-copper(II) complexes. Journal of Thermal Analysis and Calorimetry, 29, 679–686. DOI: 10.1007/bf01913525.

    Article  CAS  Google Scholar 

  • Chakravorty, A. (1974). Structural chemistry oftransition metal complexes of oximes. Coordination Chemistry Reviews, 13, 1–46. DOI: 10.1016/s0010-8545(00)80250-7.

    Article  CAS  Google Scholar 

  • Oxford Diffraction (2000). CrysAlis RED and CrysAlis CCD [computer software]. Abingdon, UK: Oxford Diffraction.

    Google Scholar 

  • Elschner, A., Heuer, H. W., Jonas, F., Kirchmeyer, S., Wehrmann, R., & Wussow, K. (2001). Gallium complexes in three-layer organic electroluminescent devices. Advanced Materials, 13, 1811–1814. DOI: 10.1002/1521-4095(200112)13:23<1811::AID-ADMA1811>3.0.CO;2-G.

    Article  CAS  Google Scholar 

  • Farrugia, L. J. (1997). ORTEP-3 for Windows — a version of ORTEP-III with a Graphical User Interface (GUI). Journal of Applied Crystallography, 30, 565. DOI: 10.1107/s0021889897003117.

    Article  CAS  Google Scholar 

  • Hall, D. B., Underhill, P., & Torkelson, J. M. (1998). Spin coating of thin and ultrathin polymer films. Polymer Engineering & Science, 38, 2039–2045. DOI: 10.1002/pen.10373.

    Article  CAS  Google Scholar 

  • Hudák, A., & Košturiak, A. (1999). Preparation, IR characterization and thermal properties of some metal complexes of isatin-3-oxime. Journal of Thermal Analysis and Calorimetry, 58, 579–587. DOI: 10.1023/a:1010148310379.

    Article  Google Scholar 

  • Huh, P. H., Yang, J. Y., & Kim, S. C. (2012). Facile formation of nanostructured 1D and 2D arrays of CuO islands. RSC Advances, 2, 5491–5494. DOI: 10.1039/c2ra20097j.

    Article  CAS  Google Scholar 

  • Ji, Z. G., Yuan, Y. H., Yuan, Y., & Wang, C. (2006). Reactive DC magnetron deposition of copper nitride films for write-once optical recording. Materials Letters, 60, 3758–3760. DOI: 10.1016/j.matlet.2006.03.107.

    Article  CAS  Google Scholar 

  • Juza, R., & Hahn, H. (1939). Kupfernitrid Metallamide und Metallnitride. VII. Zeitschrift für Anorganische und Allgemeine Chemie, 241, 172–178. DOI: 10.1002/zaac.19392410204. (in German)

    Article  CAS  Google Scholar 

  • Juza, R., & Rabenau, A. (1956). Das elektrische Leitvermöogen einiger Metallnitride. Zeitschrift für Anorganische und Allgemeine Chemie, 285, 212–220. DOI: 10.1002/zaac.19562850314. (in German)

    Article  CAS  Google Scholar 

  • Kida, T., Oka, T., Nagano, M., Ishiwata, Y., & Zheng, X. G. (2007). Synthesis and application of stable copper oxide nanoparticle suspensions for nanoparticulate film fabrication. Journal of the American Ceramic Society, 90, 107–110. DOI: 10.1111/j.1551-2916.2006.01402.x.

    Article  CAS  Google Scholar 

  • Kim, S. G., Hagura, N., Iskandar, F., Yabuki, A., & Okuyama, K. (2008). Multilayer film deposition of Ag and SiO2nanoparticles using a spin coating process. Thin Solid Films, 516, 8721–8725. DOI: 10.1016/j.tsf.2008.05.053.

    Article  CAS  Google Scholar 

  • Koumousi, E. S., Raptopoulou, C. P., Perlepes, S. P., Escuer, A., & Stamatatos, T. C. (2010). Strong antiferromagnetic coupling in doubly N,O oximato-bridged dinuclear copper(II) complexes. Polyhedron, 29, 204–211. DOI: 10.1016/j.poly.2009.07.010.

    Article  CAS  Google Scholar 

  • Li, Q., Mei, P., & Xiang, J. (2006). Di-µ-chloro-bis[chloro (phenyl 2-pyridyl ketone oxime-κ2N, N′)copper(II)]. Acta Crystallographica Section E, 62, m2348–m2349. DOI: 10.1107/s1600536806033836.

    Article  Google Scholar 

  • Liu, C. H., & Liu, C. F. (1961). Hetero-binuclear chelates of copper(II) and silver(I). Journal of the American Chemical Society, 83, 4167–4169. DOI: 10.1021/ja01481a015.

    Article  CAS  Google Scholar 

  • Liu, G. X., Yang, H., Nishihara, S., & Ren, X. M. (2010). A trinuclear Cu(II) complex from the use of phenyl 2-pyridyl ketoxime: Structure and magnetic behavior. Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 40, 421–424. DOI: 10.1080/15533174.2010.492557.

    CAS  Google Scholar 

  • Meek, T. L., & Cheney, G. E. (1965). The copper(II) synphenyl-2-pyridyl ketoxime system. Part I. Canadian Journal of Chemistry, 43, 64–74. DOI: 10.1139/v65-009.

    Article  CAS  Google Scholar 

  • Milios, C. J., Kefalloniti, E., Raptopoulou, C. P., Terzis, A., Escuer, A., Vicente, R., & Perlepes, S. P. (2004). 2-Pyridinealdoxime [(py)CHNOH] in manganese(II) carboxylate chemistry: mononuclear, dinuclear, tetranuclear and polymeric complexes, and partial transformation of (py)CHNOH to picolinate(−1). Polyhedron, 23, 83–95. DOI: 10.1016/j.poly.2003.09.009.

    Article  CAS  Google Scholar 

  • Milios, C. J., Stamatatos, T. C., & Perlepes, S. P. (2006). The coordination chemistry of pyridyl oximes. Polyhedron, 25, 134–194. DOI: 10.1016/j.poly.2005.07.022.

    Article  CAS  Google Scholar 

  • Mohan, M., & Paramhans, B. D. (1980). Transition metal chemistry of oxime-containing ligands, part XI. Copper(II) complexes of syn-phenyl-2-pyridylketoxime and syn-methyl-2-pyridylketoxime. Transition Metal Chemistry, 5, 113–117. DOI: 10.1007/bf01396885.

    Article  CAS  Google Scholar 

  • Nasui, M., Mos, R. B., Petrisor, T., Jr., Gabor, M. S., Varga, R. A., Ciontea, L., & Petrisor, T. (2011). Synthesis, crystal structure and thermal decomposition of a new copper propionate [Cu(CH3CH2COO)2] · 2H2O. Journal of Analytical and Applied Pyrolysis, 92, 439–444. DOI: 10.1016/j.jaap.2011.08.005.

    Article  CAS  Google Scholar 

  • Navío, C., Alvarez, J., Capitan, M. J., Camarero, J., & Miranda, R. (2009). Thermal stability of Cu and Fe nitrides and their applications for writing locally spin valves. Applied Physics Letters, 94, 263112. DOI: 10.1063/1.3159630.

    Article  Google Scholar 

  • Paniconi, G., Stoeva, Z., Doberstein, H., Smith, R. I., Gallagher, B. L., & Gregory, D. H. (2007). Structural chemistry of Cu3N powders obtained by ammonolysis reactions. Solid State Sciences, 9, 907–913. DOI: 10.1016/j.solidstatesciences.2007.03.017.

    Article  CAS  Google Scholar 

  • Partridge, A., Toussaint, S. L. G., & Flipse, C. F. J. (1996). An AFM investigation of the deposition of nanometer-sized rhodium and copper clusters by spin coating. Applied Surface Science, 103, 127–140. DOI: 10.1016/0169-4332(96)00520-x.

    Article  CAS  Google Scholar 

  • Prasad, R. (2003). Mechanism and kinetics of thermal decomposition of ammoniacal complex of copper oxalate. Thermochimica Acta, 406, 99–104. DOI: 10.1016/s0040-6031(03)00225-9.

    Article  CAS  Google Scholar 

  • Prathapachandra Kurup, M. R., Chandra, S. V., & Muraleedharan, K. (2000). Synthesis, spectral and thermal studies of o-vanillin oxime complexes of zinc(II), cadmium(II) and mercury(II). Journal of Thermal Analysis and Calorimetry, 61, 909–914. DOI: 10.1023/a:1010154810885.

    Article  Google Scholar 

  • Salonen, M., Saarinen, H., & Orama, M. (2003). Formation of zinc(II) and cadmium(II) complexes with pyridine oxime ligands in aqueous solution. Journal of Coordination Chemistry, 56, 1041–1047. DOI: 10.1080/00958970310001596737.

    Article  CAS  Google Scholar 

  • Sathaye, S. D., Patil, K. R., Kulkarni, S. D., Bakre, P. P., Pradhan, S. D., Sarwade, B. D., & Shintre, S. N. (2003). Modification of spin coating method and its application to grow thin films of cobalt ferrite. Journal of Materials Science, 38, 29–33. DOI: 10.1023/a:1021101529855.

    Article  CAS  Google Scholar 

  • Sceney, C. G., Hill, J. O., & Magee, R. J. (1975). Thermal analysis of copper dithiocarbamates. Thermochimica Acta, 11, 301–306. DOI: 10.1016/0040-6031(75)85099-4.

    Article  CAS  Google Scholar 

  • Schubert, D. W., & Dunkel, T. (2003). Spin coating from a molecular point of view: its concentration regimes, influence of molar mass and distribution. Materials Research Innovations, 7, 314–321. DOI: 10.1007/s10019-003-0270-2.

    Article  CAS  Google Scholar 

  • Sheldrick, G. M. (2008). A short history of SHELX. Acta Crystallographica Section A, 64, 112–122. DOI: 10.1107/s0108767307043930.

    CAS  Google Scholar 

  • Singh, K. (1971). Magnetic and spectroscopic studies on cupric azide. Transactions of the Faraday Society, 67, 2436–2444. DOI: 10.1039/tf9716702436.

    Article  CAS  Google Scholar 

  • Wang, J., Chen, J. T., Yuan, X. M., Wu, Z. G., Miao, B. B., & Yan, P. X. (2006). Copper nitride (Cu3N) thin films deposited by RF magnetron sputtering. Journal of Crystal Growth, 286, 407–412. DOI: 10.1016/j.jcrysgro.2005.10.107.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Faculty of Chemistry, Nicolaus Copernicus University, 87-100, Toruń, Poland

    Robert Szczęsny, Tadeusz M. Muzioł & Edward Szłyk

  2. WestCHEM, School of Chemistry, University of Glasgow, Glasgow, G12 8QQ, UK

    Duncan H. Gregory

Authors
  1. Robert Szczęsny
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tadeusz M. Muzioł
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Duncan H. Gregory
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Edward Szłyk
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Robert Szczęsny.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Szczęsny, R., Muzioł, T.M., Gregory, D.H. et al. Structural and thermal characterization of copper(II) complexes with phenyl-2-pyridylketoxime and deposition of thin films by spin coating. Chem. Pap. 69, 569–579 (2015). https://doi.org/10.1515/chempap-2015-0065

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1515/chempap-2015-0065

Keywords

Search

Navigation