Novel homo- and heterobinuclear ball-type phthalocyanines: synthesis and electrochemical, electrical, EPR and MCD spectral properties

• Published in: Dalton transactions : an international journal of inorganic chemistry 2010-09, Vol.39 (35), p.8143-8152
• Main Authors: Odaba, Zafer, Dumluda, Fatih, Özkaya, Ali R za, Yamauchi, Seigo, Kobayashi, Nagao, Bekaro lu, Özer
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c0dt00398k

The mononuclear Fe( ii ) phthalocyanine 2 and ball-type homobinuclear Fe( ii )-Fe( ii ) and Cu( ii )-Cu( ii ) phthalocyanines, 3 and 4 respectively, were synthesized from the corresponding 4,4′-[1,1′-methylenebis-(naphthalene-2,1-diyl)]bis(oxy)diphthalonitrile 1 , and then ball-type heterobinuclear Fe( ii )-Cu( ii ) phthalocyanine 5 was synthesized from 2 . The novel compounds 4 and 5 have been characterized by elemental analysis, UV/vis, IR and MALDI-TOF mass spectroscopies. Electron paramagnetic resonance and magnetic circular dichroism measurements of 3 , 4 and 5 were also examined. The voltammetric measurements of the complexes showed the formation of various electrochemically stable ligand- and metal-based mixed-valence species, due to the intramolecular interactions between the two MPc units, especially in ball-type binuclear iron( ii ) phthalocyanine. Impedance spectroscopy and d.c. conductivity measurements of 4 and 5 were performed as a function of temperature (295-523 K) and frequency (40-10 5 Hz). While room temperature impedance spectra consist of a curved line, a transformation into a full semicircle with increasing temperature was observed for both compounds. Electron paramagnetic resonance, magnetic circular dichroism, electrochemical and electrical measurements of ball-type Cu( ii )-Cu( ii ), Fe( ii )-Fe( ii ) and Fe( ii )-Cu( ii ) phthalocyanines were performed and discussed.