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Serendipity has been a major player in most dye discoveries, and phthalocyanines are no exception. The true account of their discovery in 1928 is given using information provided by one of the individuals involved (Ron Greig). One of the inventors, Drescher, after making a key observation as to the nature of the insoluble blue impurity formed in the routine manufacture of phthalimide from phthalic anhydride, was killed weeks later when, on his beloved Sunbeam motorcycle, he had a head-on collision with a steamroller on his way to work. The unique properties of phthalocyanine dyes and pigments make them the colorant of choice for most blue and green colours. Thus most blue and green cars, including sports cars, are coloured by phthalocyanine pigments. In addition to these traditional uses, phthalocyanines are also finding extensive use in modern hi-tech areas. They are used for their colour as, for example, cyan dyes in ink jet printing, and in colourless applications such as infrared absorbers in security. The discovery, traditional and hitech applications of phthalocyanines are described in detail in this paper.
A new dyad 9(ZnP-P) has been synthesized linking 5,15-bis(4-carboxyphenyl)-10,20-bis(4-nitrophenyl) porphyrin 4(P) and Zn(II) 5-(4-aminophenyl)-10,15,20-tris(4-methoxylphenyl) porphyrin 8(ZnP) by an amide bond. The structural moieties of dyad 9(ZnP-P) present both different singlet state energy and redox properties. Dyad 9 was designed to improve the intramolecular electron transfer capacity. The ZnP moiety bears electron-donating methoxy groups and a zinc ion, while the other porphyrin structure, P, is substituted by electron-withdrawing nitro groups. On the other hand, structure P bears a carboxylic acid group, which is able to benefit from the orientation of dyad 9 adsorbed on the SnO2 electrode. Absorption spectroscopic studies indicated only a very weak interaction between the chromophores in the ground state. The fluorescence analysis shows that both porphyrin moieties in dyad 9 are strongly quenched and that the quenching increases in a polar solvent. The ZnP moiety acts like an antenna for porphyrin P, but, singlet-singlet energy transfer is not complete. Thermodynamically, dyad 9 presents a high capacity to form the photoinduced charge-separated state, ZnP·+-P·-. Dyad 9 sensitizes the SnO2 electrode and the photocurrent action spectrum closely matches the absorption spectrum, which confirms that light absorption by dyad is the initial step in the charge transfer mechanism. The photocurrent efficiency of dyad 9 is considerably higher than those of porphyrin monomers used as models of ZnP and P structures. Two processes may be contributing to enhance the charge injection efficiency in dyad 9; one involves an antenna effect that produces energy transfer from ZnP to P and the other includes electron transfer from the ZnP moiety to the photooxidizable free-base P. This dyad design, with P in direct contact with the substrate through the free carboxylic acid group, is a promising architecture of organic material for spectral sensitization of semiconductor solar cells.
Novel complexes of cobalt(II) with sulfonated derivatives of phthalocyanines are synthesized. The influence of the sulfonated group's number in peripheral substituent on solubility of macrocycle and ability to form ordered structures in solution is showed. Transition from H-aggregates to monomeric phthalocyanine structures and sandwich-type dimers was found during formation of metallophthalocyanine complexes with 1,4-diazabicyclo[2.2.2]octane. The catalytic activity of metallophthalocyanines was studied on the model of Merox process.