Polymeric phthalocyanines and their precursors, 12. Reversible reduction and reoxidation of thin films of octacyanophthalocyanine in polymer matrices

Abstract

Thin films containing 1 -100 pg 2,3,9,10,16,17,23,24-phthalocyanineoctacarbonitrile (1) and 10 -100 pg poly(N4nylcarbazole) (2) resp. the polyimide 3 were prepared on gold substrates through casting from solution. Smooth green coloured films were obtained. According to VIS spectra molecules of 1 are aggregated within the polymer matrices. Cyclic voltammetric measurements were carried out in 0,s M sulfuric acid. Mixed films of 1 and 2 show remarkably stable electrochromic redox behaviour and the charge exchanged in the cathodic and anodic wave, respectively, was found to be between 2,3 and 2,7 F/mol for scan rates up to 400 mV . s -. For mixed films of 1 and 3 with lower amount of 1 or increasing layer thickness the reduction and reoxidation appears to be a diffusion controlled process. a) Part 10: cf.'), part 11: cf.").

Phthalocyanines in Macromolecular Phases - Methods of Synthesis and Properties of the Materials

“…[1] The mechanism of film growth according to method C was discussed in the literature. [63,64] After formation of the first few layers of polymeric phthalocyanines, copper atoms diffuse from the copper film to the growing polymer film surface in order to react with tetracarbonitrile 5 to give 9 and, subsequently, to oligomeric and polymeric phthalocyanines (Equation (8)). By means of ESCA spectroscopy, L0.7% of free Cu in the polymeric films were found.…”

Synthesis of polymeric and low molecular weight phthalocyanines from nitriles and metal carbonyls on SiO2 and TiO2 and catalytic activities in the sulfide oxidation

“…Only in the case of Cu or CuCl 2 in the reaction with tetracarbonitriles structurally uniform 1, 2 with nitrile end groups and a molecular weight up to infinite were obtained. It was pointed out in the introduction that these experiences were extended to prepare thin films by the gas-phase reaction of tetracarbonitriles with a vapor-deposited Cu-film [4][5][6][7][8][9][10][11] or Co 2 -loaded inorganic carriers [12]. The process of chemical vapor deposition of thin reactive metal films by decomposition of metal carbonyls [26,27] was now used for the first time for the preparation of coatings of metals and also metal carbonyls on inorganic carriers followed by reactions with nitriles under conditions of phthalocyanine formation.…”

“…In the reactions with nitriles (4-6) different metal carbonyls and some organometallic compounds of Co, Mo, W and Cr on SiO 2 and TiO 2 are employed. Some low molecular analogous phthalocyanines have been described [21][22][23], and some reactions of metal carbonyls such as Fe(CO) 5 with dinitriles are known (see for example [24,25]). It is the aim of this work to study fundamentally the reactivity and the formation of phthalocyanines from the mentioned metal precursors on the inorganic carriers.…”

“…One method uses in the first step the vapor deposition of copper on quartz, basal plane pyrolytic graphite, Ti plates or cleaved KCl crystals followed by reaction with tetracarbonitriles (1,2,4,5-tetracyanobenzene (4), diphthalonitriles such as 1,4-bis-(3,4-dicyanophenoxy)-benzene (5)) at $300 -400°C for $4-24 h in a closed bomb vessel [4][5][6][7][8][9][10][11]. Few reports describe the reaction of metal ion (Co 2 ) loaded powdered inorganic carriers (SiO 2 , g-Al 2 O 3 or active carbon) with tetracarbonitriles at higher temperatures in a closed bomb vessel under formation of coatings of 1 or 2 [12].…”

Highly Sensitive Electrochemical Sensor for Nitric Oxide Using the Self‐Assembled Monolayer of 1,8,15,22‐Tetraaminophthalocyanatocobalt(II) on Glassy Carbon Electrode

“…While designing the MPc based electrochemical sensor, fabrication of the electrode surface plays a crucial role. Vapor phase deposition [3], casting [4], electropolymerization [5] and self-assembly [6 -8] methods have been used for the modification of electrode surface with MPcs. Among these methods, self-assembly method has several advantages over other methods including ease in preparation, good electronic communication with the underlying electrode and complete involvement of the self-assembled molecules in the electrochemical reactions [9].…”