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Zeitschrift für Naturforschung B

A Journal of Chemical Sciences


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Volume 72, Issue 8

Issues

Synthesis and purification of metallooctachlorophthalocyanines

Tobias Rüffer
  • Corresponding author
  • Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Anorganische Chemie, Straße der Nationen 62, D-09111 Chemnitz, Germany
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  • Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Anorganische Chemie, D-09111 Chemnitz, Germany
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Published Online: 2017-08-05 | DOI: https://doi.org/10.1515/znb-2017-0068

Abstract

A detailed synthetic procedure based on the use of urea, dichlorophthalic acid, respective transition metal halides and [NH4]2[MoO4] as a catalyst in the melt or by using 1,2,4-trichlorobenzene as a high-boiling inert solvent is described to gain 2,3,9,10,16,17,23,24-metallooctachlorophthalocyanines (MPcCl8 compounds with M=Mn, Fe, Co, Ni, Cu). In cases that a first purification by subsequent treatment of the crude materials with HCl, NaOH and HCl would not give rise to analytically pure compounds, a second novel purification by using pyridine is described. The degree of purity, exceeding always 98%, is determined by thermogravimetric analysis. Comparative IR, UV/Vis and PXRD studies of the MPcCl8 compounds are reported.

This article offers supplementary material which is provided at the end of the article.

Keywords: IR spectroscopy; powder X-ray diffraction; thermogravimetric analysis; urea melt method; UV/Vis spectroscopy

References

  • [1]

    W. J. Baker, K. Ambal, D. P. Waters, R. Baarda, H. Morishita, K. van Schooten, D. R. McCarney, J. M. Lupton, C. Boehme, Nat. Commun. 2012, 3, 898.Google Scholar

  • [2]

    T. Reichert, T. P. I. Saragi, Appl. Phys. Lett. 2011, 98, 063307.Google Scholar

  • [3]

    T. D. Nguyen, E. Ehrenfreund, Z. V. Vardeny, Science 2012, 337, 204.Google Scholar

  • [4]

    Z. H. Xiong, D. Wu, Z. V. Vardeny, J. Shi, Nature 2004, 427, 821.Google Scholar

  • [5]

    V. Dediu, M. Murgia, F. C. Matacotta, S. Barbanera, C. Taliani, C. Solid State Commun. 2002, 122, 181.Google Scholar

  • [6]

    B. Göhler, V. Hamelbeck, T. Z. Markus, M. Kettner, G. F. Hanne, Z. Vager, R. Naaman, H. Zacharias, Science 2011, 331, 894.Google Scholar

  • [7]

    M. Urdampilleta, S. Klyatskaya, J.-P. Cleuziou, M. Ruben, W. Wernsdorfer, Nat. Mater. 2011, 10, 502.Google Scholar

  • [8]

    S. Sanvito, Nat. Phys. 2010, 6, 562.Google Scholar

  • [9]

    S. Lindner, M. Knupfer, R. Friedrich, T. Hahn, J. Kortus, Phys. Rev. Lett. 2012, 109, 027601.Google Scholar

  • [10]

    For example, S. Lindner, B. Mahns, A. König, F. Roth, M. Knupfer, R. Friedrich, T. Hahn, J. Kortus, Chem. Phys. 2013, 138, 024707.Google Scholar

  • [11]

    R. Friedrich, B. Kersting J. Kortus, Phys. Rev. B 2013, 88, 155327.Google Scholar

  • [12]

    M. Serri, W. Wu, L. R. Fleet, N. M. Harrison, C. F. Hirjibedehedin, C. W. M. Kay, A. J. Fisher, G. Aeppli, S. Heutz, Nat. Commun. 2014, 5, 3079.Google Scholar

  • [13]

    N. Safari, P. R. Jamaat, M. Pirouzmand, A. Shaabani, J. Porphyrins Phthalocyanines 2004, 8, 1209.Google Scholar

  • [14]

    N. Safari, P. R. Jamaat, S. A. Shirvan, S. Shoghpour, A. Ebadi, M. DarVishi, A. Shaabani, J. Porphyrins Phthalocyanines 2005, 9, 256.Google Scholar

  • [15]

    DMSO=dimethyl sulfoxide. CAS: 67-68-5. According to, for example, the “Gestis Stoffdatenbank” under http://gestis.itrust.de/nxt/gateway.dll?f=templates&fn=default.htm&vid=gestisdeu:sdbdeu the b.p. of DMSO is 189°C. From here on the action to be performed assigned as “to reflux” indicates: To heat a solvent to its boiling point to such an extent that the evaporated solvent condenses on a reflux condenser and drops back to the solution.

  • [16]

    B. N. Achar, T. M. M. Kumar, K. S. Lokesh, J. Coord. Chem. 2007, 60, 1833.Google Scholar

  • [17]

    As described later on in this report, one byproduct of the synthesis of MPcs via the urea method is 1,3,5-triazine-2,4,6-triol (CAS: 108-80-5), conventionally referred to as “cyanuric acid” (CA). According to: https://www.merckmillipore.com/INTERSHOP/web/WFS/Merck-DE-Site/de_DE/-/EUR/ProcessMSDS-Start;pgid=1YpMKfaYduNSRpEoLGRgbI7200006zq7dkH1;sid=X-TZtCtxc5e1tHMm-xHJPMUk5mIb627aBjjiZfoVPFjFhKMfhybWJ4sZcG3_-HtNlBL3rfgHnNkgHAO_dVKrkgVXPUVdvThYUPLRyfTNPewtdiEKhD2emPhP3DpS-N2swfJR2vOz14oBduhMpkzTz_Co?PlainSKU=MDA_CHEM-820358&Origin=PDP, the melting point is ca. 320–330°C. IR spectra of CA in nujol mull can be found in the online freely available Spectral Database for Organic Compounds (SDBS) either under the CAS or SDBS number (SDBS No.: 2043) via the link http://sdbs.db.aist.go.jp/sdbs/cgi-bin/cre_index.cgi. Further SDBS numbers: CuPc (4418), NiPc (17185), CoPc (24499), FePc (5223), MnPc (17255).

  • [18]

    K. H. Thiele in Lehrwerk Chemie, Arbeitsbuch 7, Reaktionsverhalten und Syntheseprinzipien, 3. unveränderte Auflage; VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1989; p. 218. “5 g phthalic acid, 1 g CuCl2·2H2O, 25 g urea and approximately 50 mg [NH4]2[MoO4] as catalyst are accurately mortared. The mixture is heated next in a round bottom flask with the help of an oil or sand bath for six hours to an internal temperature of 180°C. After cooling down the mixture is cooked with 2 M HCl and vacuum-sucked. The filter cake is treated for approximately 10 min with cold 2M NaOH and again vacuum-sucked. The obtained blue material is cooked again with 2 M HCl, filtrated and washed until the filtrate is free of chloride ions and dried in an exsicattor.”Google Scholar

  • [19]

    C. C. Leznoff in Synthesis of Metal-Free Substituted Phthalocyanines in Phthalocyanines: Properties and Applications, Vol. 1 (Eds.: C. C. Leznoff, A. B. P. Lever), VCH, Weinheim, 1989, chapter 1, p. 16, and references cited there.Google Scholar

  • [20]

    For example, J. M. Robertson, J. Chem. Soc. 1935, 615.CrossrefGoogle Scholar

  • [21]

    M. Hanack, R. Thies, Chem. Ber. 1988, 121, 1225.Google Scholar

  • [22]

    F. H. Moser, A. L. Thomas, Phthalocyanine Compounds, American Chemical Society, Monograph Series, Reinhold Publishing Corporation, New York, 1963, p. 34.Google Scholar

  • [23]

    K. Sivashankar, Proc. Indian Acad. Sci. (Chem. Sci.) 2000, 112, 607.Google Scholar

  • [24]

    A. A. Ebert Jr., H. B. Gottlieb, J. Am. Chem. Soc. 1952, 74, 2806.Google Scholar

  • [25]

    Cf.: http://www.elementar.de/de/produkte/organische-elementaranalyse/vario-micro-cube.html “Quantitative decomposition up to 1200°C – with 10 years warranty on the furnace. (1800°C at the moment of combustion and by using tin capsules.) This is pre-requisite for 100 % retrieval and analytical accuracy also for difficult combustable samples. The jet injection of oxygen realizes a high local concentration at the decomposition spot together with an economical gas consumption” Citation taken accessed 24 July 2017.

  • [26]

    N. B. McKeown, Phthalocyanine Materials Synthesis, Structure and Function, Cambridge University Press, Cambridge, 1998, chapters 4.1 to 4.3.Google Scholar

  • [27]

    K. Huthmacher, D. Most, Cyanuric Acid and Cyanuric Chloride in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005.Google Scholar

  • [28]

    V. N. Nemykin, E. A. Lukyanets, ARKIVOC 2010, (i), 136.Google Scholar

  • [29]

    P. Zimcik, A. Malkova, L. Hruba, M. Miletin, V. Novakova, Dyes Pigm. 2017, 136, 715.Google Scholar

  • [30]

    P. M. Reintanz, R. Guthardt, C. Bruhn, F. Mohr, U. Siemeling, Eur. J. Inorg. Chem. 2016, 36, 5610.Google Scholar

  • [31]

    J. Janczak, R. Kubiak, M. Sledz, H. Borrmann, Y. Grin, Polyhedron 2003, 22, 2689.Google Scholar

  • [32]

    R. Friedrich, T. Hahn, J. Kortus, M. Fronk, F. Haidu, G. Salvan, D. R. T. Zahn, M. Schlesinger, M. Mehring, F. Roth, B. Mahns, M. Knupfer, J. Chem. Phys. 2012, 136, 064704.Google Scholar

  • [33]

    H. A. Jahn, E. Teller, Proc. R. Soc. London, Ser. A 1937, 161, 220.Google Scholar

  • [34]

    J. Janczak, R. Kubiak, Inorg. Chim. Acta 2003, 342, 64.Google Scholar

  • [35]

    Cf. for example the Author guides of the ACS Journal Inorganic Chemisty: http://pubs.acs.org/paragonplus/submission/inocaj/inocaj_authguide.pdf.

About the article

Received: 2017-04-20

Accepted: 2017-05-18

Published Online: 2017-08-05

Published in Print: 2017-08-28


Author contributions: TR and HL conceived and designed the experiments and wrote the paper; DN performed experiments to synthesize, purify and characterize repetitively all pristine MPcs and MPcCl8 compounds reported here by the urea melt method and in part by using 1,2,4-trichlorobenzene as an inert solvent, whereby ZJ and AT analyzed the data; NU and AK synthesized, purified and analyzed repetitively MPcCl8 compounds by using 1,2,4-trichlorobenzene as an inert solvent under various reaction conditions; AG conceived, designed and carried out experiments to modify the crystallinity of pristine MPcs and MPcCl8 compounds reported here; LM measured PXRD data and created corresponding figures accordingly; MM analyzed PXRD data and is thanked for fruitful comments on the paper.

Conflicts of Interest: The authors declare no conflict of interest.


Citation Information: Zeitschrift für Naturforschung B, Volume 72, Issue 8, Pages 589–601, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: https://doi.org/10.1515/znb-2017-0068.

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