Copper phthalocyanine polymers, structure

The synthesis of copper phthalocyanine polymers was reported in the 1950s by Marvel and Rassweiler " and Drinkard and Bailar." Bailar reported that the reaction of pyromellitic dianhydride, copper(II), and urea in the presence of a catalytic amount of ammonium molybdate resulted in the production of oligomeric copper phthalocyanines." While it was postulated that the polymers had a linear structure (5), it is also possible that the polymer has a sheetlike structure (6). A number attempts were made to determine the molecular weights of these materials however, accurate values were not obtained. 

FIGURE 8.1 Molecular structures of some common conjugated polymers and small molecules (a) poly(p-phenylene vinylene), (b) polythiophenes, (c) MEH-PPV, (d) P3HT, (e) copper phthalocyanine, and (f) pentacene. 

Polymetallophthalocyanines are structurally similar to polymetalloporphyrins however, the presence of an additional four arenes and four nitrogen atoms in their structures has a strong influence on their UV-visible spectra In 1958, Marvel and Rassweiler reported the synthesis of copper-coordinated phthalocyanine polymers, where polymerization occurred through the aromatic rings Polymer 33 is an... 

The impetus for the preparation of polymeric metal phthalocyanines is repeatedly traced to an early report on the thermal stability of copper phthalocyanine 24). Dent and Linstead 24) described it to be exceptionally resistant to heat and at about 580°C it may be sublimed at low pressure in an atmosphere of nitrogen or carbon dioxide. This description served to suggest to several groups that incorporation of a metal phthalocyanine structure into a polymeric repeat unit would yield polymers of exceptional thermal stability. 

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