Aggregation of Octa-[(4 '-benzo-15-crown-5)oxy]phthalocyanines in the Polar Solvents

作者：Ovsyannikova Elena V; Shiryaev Andrey A; Kalashnikova Irina P; Baulin Vladimir E; Tsivadze Asian Yu; Andreev Vladimir N; Alpatova Ninel M^*

来源：Macroheterocycles, 2013, 6(3): 274-281.

DOI：10.6060/mhc130745a

• Octa-[(4 '-benzo-15-crown-5)oxy]phthalocyanine
• the complexes with zinc
• magnesium and cobalt
• dissolution
• aggregation
• amorphous phase
• crystalline phase

We continue to study the possibility of octa-[(4'-benzo-15-crown-5)oxy]phthalocyanines (Mcr(8)Pcs) to be dissolved in some polar solvents (epsilon>30). On the example of cobalt derivative of phthalocyanine it is shown that, in the row dimethylformamide-dimethylsulfoxide-propylene carbonate-water (both in the individual solvents and salt solutions) a possibility of dissolution is determined by complex combination of non-covalent interactions between phthalocyanine molecules or between these molecules and a medium. The predominant interactions are as follows: the hydrophobic interactions of phthalocyanine rings with hydrophobic solvent fragments, donor-acceptor interactions of salt cations with crown fragments of phthalocyanines, and stacking of conjugated electron systems of phthalocyanines rings. In addition, a solvating ability of solvent towards the cations of dissolved salts is of importance. In the studied systems (except for dimethylformamide), the most effective reagent is a potassium cation. Electron spectroscopy and small-angle X-ray scattering methods were used for investigating the effect of phthalocyanine central ion on the behavior of Mcr(8)Pcs in aqueous solutions of potassium salts. The preparation of solutions with the concentration of 10(-4) M takes a long time (weeks). Along with the solution, all freshly prepared aqueous solutions of Mcr(8)Pc (M = H-2, Zn, Mg) contain solid particles (approximately 25 nm in diameter). The most slightly soluble compound is Mgcr(8)Pc, which contains not only an amorphous phase but a crystalline phase as well. The latter hinders the dye dissolution with the formation of solution. It should be noted that the amorphous phase provides a quickly precipitating suspension whereas the crystalline phase forms long-lived suspension.

• 出版日期2013-10