Synthesis and electrochemical, electrical and gas sensing properties of novel mononuclear metal-free, Zn(II), Ni(II), Co(II), Cu(II), Lu(III) and double-decker Lu(III) phthalocyanines substituted with 2-(2H-1,2,3-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl) phenoxy

• Published in: Synthetic metals Vol. 161; no. 1-2; pp. 112 - 123
• Main Authors: Gümrükçü, Gülşah, Özgür, Mahmure Üstün, Altındal, Ahmet, Özkaya, Ali Rıza, Salih, Bekir, Bekaroğlu, Özer
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01-01-2011; Elsevier
• Subjects: Chemistry; Conductivity; Copper; Direct current; Double decker; Electrochemistry; Electrochemistry–spectroelectrochemistry; Exact sciences and technology; Gas sensing; Gas sensors; General and physical chemistry; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Impedance spectroscopy; Kinetics and mechanisms; Lutetium double decker; Nickel; Noncondensed benzenic compounds; Organic chemistry; Phthalocyanine; Preparations and properties; Reactivity and mechanisms; Synthesis; Toluene; Voltammetry; Conductivity; Phthalocyanine; Gas sensing; Synthesis; Lutetium double decker; Electrochemistry–spectroelectrochemistry; Copper II; Benzotriazole derivatives; Fourier transformation; Transition element complexes; Chemical analysis; Electrical conductivity; Nickel II; Nitrile; Film; Nitrogen heterocycle; Electrochemistry-spectroelectrochemistry; Lutetium III; Temperature effect; NMR spectrometry; Matrix assisted laser desorption ionization; Characterization; Hydrogen 1; Cyclic voltammetry; Cobalt II; Reaction mechanism; Redox system; Chemical synthesis; Spectroelectrochemistry; Nucleophilic reaction; Electrical properties; Zinc II; Toluene; Measurement sensor; Infrared spectrometry; Time of flight method; Metallophthalocyanine; Electrochemistry; Phenols; Impedance; Gas sensors; Mass spectrometry; Ultraviolet visible spectrometry
• ISSN: 0379-6779; 1879-3290
• DOI: 10.1016/j.synthmet.2010.11.006

Novel metallophthalocyanines 4–8 (M=Zn, Ni, Co, Cu, Lu, respectively), metal free 9 and double decker Lu(III) phthalocyanine 10 with four peripheral 2-(2H-1,2,3-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenoxy groups were synthesized by cyclotetramerisation of the phthalonitrile. Their electrochemical, electrical and gas sensing properties were also investigated. [Display omitted]
▶ The CBH model is the dominant conduction mechanism for the films of compounds 4–10. ▶ The films of compounds 4–7 have reversible sensor response to toluene vapor. ▶ Unusual redox behaviour of double decker LuPc2 in comparison with the others. ▶ Impedance spectroscopy and dc conductivity measurements were performed.
A new mono substituted phthalonitrile derivative 3 was prepared by a nucleophilic displacement reaction of 4-nitrophthalonitrile with 2-(2H-1,2,3-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol. Novel metallophthalocyanines 4–8 (M=Zn, Ni, Co, Cu, Lu, respectively), metal free 9 and double decker Lu(III) phthalocyanine 10 with four peripheral 2-(2H-1,2,3-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenoxy groups were synthesized by cyclotetramerisation of the phthalonitrile and characterized by elemental analyses, FTIR, 1H NMR, UV–vis and MALDI-TOF MS spectral data. Cyclic voltammetry, differential pulse voltammetry and in situ spectroelectrochemistry of the phthalocyanine compounds have been studied. This allowed us to identify and compare metal- and phthalocyanine ring-based redox processes of the complexes. Impedance spectroscopy (IS) and dc conductivity measurements were performed as a function of temperature (300–430K) and frequency (40–105Hz.). The sensing properties of the films for toluene were also investigated. The dc results showed an activated conductivity dependence on temperature for all films. While room temperature impedance spectra consist of a curved line, a transformation into a full semicircle with increasing temperature was observed. The analysis of ac conductivity data showed that the CBH model is the dominant conduction mechanism for the electron transport in the films. While exposure to toluene has no effect on the conductivity of the film of 8–10 completely reversible sensor response to toluene only were obtained for compounds 4–7. It was also observed that the operating temperature had a considerable effect on sensing characteristics of the films.