Preparation and characterization of thin films of monomeric and polymeric octacyanophthalocyanines

Abstract

SynopsisThin films were prepared on substrates, cleavage surface of KCl single crystal, and metallic copper, by reaction of 1,2,4,5-tetracyanobenzene with the substrate at various temperatures. The films were characterized by elemental analysis, IR, and W / V I S spectroscopies. The films were observed by scanning electron microscopy. The films produced on copper a t temperatures between 300 and 400°C consisted of copper octacyanophthalocyanine and its polymer with ladder structure. The ratio of polymer to monomer increased with elevating the reaction temperature. The films were composed of ribbon-like crystals. The film produced on copper above 450°C was composed of an amorphous and continuous layer of polymeric copper phthalocyanine. The film produced on KCl a t temperatures between 250 and 350°C consisted of potassium octacyanophthalocyanine and its polymer with ladder structure. The film produced on KC1 above 450°C was polymeric potassium phthalocyanine. Those films contained more h e t a l content than that required stoichiometrical.

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

“…All reactions were performed under N 2 atmosphere or vacuum. The reactions carried out for the synthesis of polymeric phthalocyanines (1, 2) from the tetracarbonitriles (4, 5), and for comparison, for the synthesis of low molecular phthalocyanines (3) from phthalonitrile (6) with metal or metal carbonyls (W(CO) 6 , Mo(CO) 6 , Cr(CO) 6 , Co 2 (CO) 8 ) are schematically shown in Scheme 2. Tables 1 and 2 contain the reaction conditions.…”

“…Commercial phthalonitrile was purified by sublimation. Co 2 (CO) 8 , Mo(CO) 6 , W(CO) 6 , Cr(CO) 6 were used as supplied (Aldrich).…”

“…Then under inert conditions (N 2 ). To 1Á5 g of an inorganic oxide in a glass vessel of $25 mL the following amounts of metal carbonyls were added and shook at a definite temperature T 1 (Tables 1 and 2) for 3 h to allow a homogenous distribution on the carriers: 0.17 mmol W(CO) 6 , 0.3 mmol Mo(CO) 6 , 0.6 mmol Cr(CO) 6 or 0.26 mmol Co 2 (CO) 8 . The glass vessels were closed under vacuum, and then the metal carbonyls were decomposed by heating for 2 h at a definite temperature T 2 (Tables 1 and 2) as determined by differential thermal analysis.…”

“…This method was also applied for coatings of low molecular weight phthalocyanines directly on the mentioned powdered inorganic carriers [12,13]. Compared to thin films of low molecular weight phthalocyanines (3), thin films of the analogous polymers (1, 2) can exhibit better electrical conductivities, and electrochemical and photoelectrochemical properties [4,[6][7][8][9][10][11].…”

“…The synthesis and properties of polymeric phthalocyanines such as 1 or 2 from tetracarbonitriles (4 or 5) [1,2] compared to low molecular phthalocyanines (3) from dicarbonitriles (6) [3] (Scheme 1) are described only rarely. The polymers are obtained as insoluble dark-colored powders and are therefore difficult to characterize with regard to their structural uniformity.…”