Electrical and electrochemical properties of double-decker Lu(III) and Eu(III) phthalocyanines with four imidazoles and N-alkylated imidazoles

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• 作者：Ebru Yaba? ; Mustafa S¨¹l¨¹ ; Fatih Dumluda? ; Ali R?za ?zkaya ; Bekir Salih ; ?zer Bekaro?lu
• 关键词：Imidazole ; Double-decker phthalocyanines ; Lanthanide ; Electrical properties ; Electrochemistry
• 刊名：Polyhedron
• 出版年：2012
• 出版时间：25 July, 2012
• 年：2012
• 卷：42
• 期：1
• 页码：196-206
• 全文大小：1509 K

文摘

Imidazole tetrasubstituted double-decker Lu(III) (boldFont"">2) and Eu(III) (boldFont"">3) phthalocyanines have been synthesized by heating 4[(4,5-diphenyl-1H-imidazole)-2-yl-thio]phthalonitrile (boldFont"">1) with Lu(OAc)₃¡¤nH₂O or Eu(OAc)₃¡¤nH₂O in n-hexanol in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene, respectively. N-alkylated imidazole tetrasubstituted double-decker Lu(III) (boldFont"">4) and Eu(III) (boldFont"">5) phthalocyanines have been synthesized by the reaction of compounds boldFont"">2 and boldFont"">3 with hexyl bromide, in DMF in the presence of K₂CO₃, respectively. The new compounds were obtained in sufficient purity after successive washing with different solvents and were characterized by elemental analysis and ¹H NMR, UV-Vis, IR, MALDI-TOF mass and electron spin resonance spectra. Electrical measurements of the boldFont"">2-boldFont"">5 performed in a vacuum (<2 ¡Á 10^?3 mbar) in the dark between the temperatures of 295 and 523 K suggest that their films show semi-conductor behavior. It was found that, in general, ¦Ò_d.c. (boldFont"">4) > ¦Ò_d.c. (boldFont"">2) in the temperature range 295-458 K, and ¦Ò_d.c. (boldFont"">5) > ¦Ò_d.c. (boldFont"">3) in the measured temperature range. Depressed semi-circles with different radii at high temperatures in impedance spectra measurements indicated deviation from the Debye dispersion relation. The redox behaviors of the compounds were also investigated by voltammetry and in situ spectroelectrochemistry in dimethylsulfoxide with tetrabutylammonium perchlorate.