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Isotopic exchange in solid cobalt phthalocyanine—I: Thermal treatment and charge transfer interactions
Journal article

Isotopic exchange in solid cobalt phthalocyanine—I: Thermal treatment and charge transfer interactions

Mohanan Kalliat and Amar Nath
Journal of inorganic & nuclear chemistry, v 43(2), pp 271-280
1981

Abstract

Isotopic exchange of α and ß-cobalt phthalocyanine (CoPc) doped with carrier-free 57CoCl 2 was studied at different temperatures in presence, and absence of oxygen. In samples sealed in evacuated vials, the exchange is induced by electrons released from multi-depth donors. The results show that ß-CoPc has a smaller density of donors and a deeper distribution in depths, as compared to α-CoPc. The mode of population of traps with electrons (or holes) during the preparation is discussed. Thermal treatment of CoPc in air and followed by doping with 57CoCl 2 (and radiochemical analysis) gives us the magnitude of isotopic exchange induced by holes, which are injected by virtue of charge transfer interactions between molecules of CoPc and O 2. Our observations indicate that the rate of diffusion of O 2 into CoPc crystallites depends on the temperature and the period of thermal treatment. The diffusion continues well beyond 1 week even at relatively high temperatures. The concentration of the injected holes and therefore the magnitude of exchange depends on the size of particles. The diffusion and chemisorption of O 2 seems to be facilitated considerably when the microcrystallites of CoPc are suspended in oxygenated water (as compared to the dry powder). When aliquots of 57Co 2+-doped CoPc are compacted with o-chloranil or iodine, strong charge transfer interactions between CoPc, and o-chloranil, and (to a lesser extent) iodine molecules, inject high concentrations of holes and thereby induce considerable exchange. When samples of 57Co 2+-doped α- or ß-CoPc are heated in air, either detrapped electrons or injected holes may induce exchange. In ball-milled samples, consisting of very fine particles, the contributions towards exchange by electrons and holes, become additive. This amazing observation indicates that large non-equilibrium concentrations of electrons and holes co-exist for considerable lengths of time without recombination. In conclusion, the dopant 57Co 2+ in CoPc constitutes a good probe and we have obtained a wealth of information which would be difficult to obtain by purely physical measurements.

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Chemistry, Inorganic & Nuclear
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