www.rsc.org/ ab Ruthenium(II) tetra-15-crown-5-phthalocyaninate with axially coordinated molecules of pyrazine [(15C5)4Pc]Ru (pyz)2 (1) was synthesized from carbonyl complex [(15C5)4Pc]Ru(CO)(MeOH) (2),and the structure of the solvate complex (1)·6CHCl3 was revealed by the single crystal X-ray diffraction method. Analysis of crystal packing shows the essential role of weak intermolecular interactions, such as CH…π, CH…N, CH…O and CH…Cl, in the formation of stable assemblies and their organization within the crystals. The interplay between the intramolecular axial coordinated pyrazine contacts and weak intermolecular interactions of solvate molecules with crown-ether fragments provides the basis for rationalizing the observed self-assembling of molecules in solutions of tetrachloroethane and polymeric composites with polyvinylcarbazole. The self-assembling was investigated by means of UV-Vis spectroscopy, dynamic light scattering measurements, AFM and TEM techniques. The formation of nanoparticles of complex (1) from a tetrachloroethane solution after three cycles of heating to 70°C/cooling to 5°C and 2-days storage was proved. Thin films (7 µm) of polymeric composites with polyvinylcarbazole prepared from solution containing nanoparticles exhibit nonlinear optical response measured by the Z-scan technique with application of femtosecond (1030 nm) and nanosecond (1064 nm) pulse lasers.The measured third-order susceptibility (χ (3) ) of the polyvinylcarbazole composite with 4 wt% of complex (1) is equal to 1.94×10 -10 esu, while the same composite prepared without the above-described special treatment has zero susceptibility.This result proves the essential role of self-assembling in further development of nonlinear optical materials.

The information concerning the architecture of supramolecular assemblies, which are composed of ruthenium(II) tetra-15-crown-5-phthalocyaninate with axially coordinated triethylenediamine molecules, has been obtained with the application of atomic force microscopy. The ensembles are formed in Ru(II) complex solutions in chloroform and tetrachloroethane. The number of molecules and their relative orientation in supramolecular assemblies were estimated in dependence of the solvent (chloroform, tetrachloroethane) and the heating temperature. Samples fabricated after heating of the Ru(II) complexes solution in tetrachloroethane formed stable supramolecular wires of 600 nm and more in length. The third-order non-linear optical characteristics of complexes in tetrachloroethane solution were studied by the z-scanning method. Molecular polarizability of the complex is about 4.5 × 10 -32 esu. The polarizability attributed to one molecule increases by a factor of 3.6 when the individual molecule assembles into a supramolecular aggregate. , tel: +7 495-955-48-74 J. Porphyrins Phthalocyanines 2009.13:92-98. Downloaded from www.worldscientific.com by UNIVERSITY OF AUCKLAND LIBRARY -SERIALS UNIT on 03/01/15. For personal use only.

Polyvinylcarbazole (PVK) composites containing graphene in an amount of somewhat less than 0.15 wt % exhibit third order dielectric susceptibility due to the presence of graphene, as well as photoelectric and photorefractive sensitivity at 1064 nm. The photorefractive (PR) effect is known to occur in a polymer composite that possesses both photoelectric sensitivity and nonlinear optical properties. The photoelectric, nonlinear optical, and PR properties of PVK composites with graphene have been considered in this paper.

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