Synthesis, characterization, and electrochemical, spectroelectrochemical and electrical measurements of novel ball-type four 1,1′-methylenedinaphthalen-2-ol bridged metal-free, zinc(II) and cobalt(II), and metal-free clamshell phthalocyanines

Zafer Odabaş, Ahmet Altindal, Ali Riza Özkaya, Mustafa Bulut, Bekir Salih, Özer Bekaroǧlu*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

63 Citations (Scopus)

Abstract

The new ball-type bisphthalocyanines [metal-free 6, Zn(II) 7 and Co(II) 8] were synthesized from the corresponding 4,4′-[1,1′-methylenebis(naphthalene-2,1-diyl)]bis(oxy)di-phthalonitrile 4, which can be obtained from the reaction of 4-nitrophthalonitrile (2) with 1,1′-methylenedinaphthalen-2-ol 3. A novel clamshell type bisphthalocyanine 5 was synthesized from compound 4 and 4,5-bis(hexylthio)phthalonitrile 1. The novel compounds have been characterized by elemental analysis, UV/Vis, IR, 1H NMR and MALDI-TOF Mass spectroscopies. The electrochemical and spectroelectrochemical measurements showed the formation of various mixed-valence oxidation and reduction species, due to the strong intramolecular interactions between the two phthalocyanine rings, especially in the ball-type phthalocyanines. The conduction properties of the compounds have been examined by d.c. and impedance spectroscopy measurements as function of temperature and frequency. D.c. conductivity, measured between 290 and 480 K, is thermally activated with the activation energy ranging between 0.62 and 0.84 eV. The a.c. results gave a power law behaviour, σa.c. = A(T)ωs, in which the frequency exponent s decreases with temperature for 6, 7 and 8. The bulk resistance of the samples was derived from complex impedance spectra. It was found that the bulk resistance shows a typical negative temperature coefficient of resistance, decreasing with a rise in temperature, like that of a semiconductor.

Original languageEnglish
Pages (from-to)695-707
Number of pages13
JournalPolyhedron
Volume26
Issue number3
DOIs
Publication statusPublished - 10 Feb 2007
Externally publishedYes

Funding

This work was supported partly by the Turkish Academy of Sciences (TUBA), The Research Fund of Marmara University (SCIENCE-107/020603) and Scientific and Technical Research Council of Turkey (TUBITAK) [TBAG-HD/50 (105T262)].

FundersFunder number
TUBA
TUBITAK105T262
Türkiye Bilimsel ve Teknolojik Araştirma Kurumu
Türkiye Bilimler Akademisi
Marmara ÜniversitesiSCIENCE-107/020603

    Keywords

    • Ball type
    • Bisphthalocyanine
    • Clamshell
    • Impedance spectroscopy
    • Spectroelectrochemistry
    • Synthesis

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