Ekaterina Semenishyna Ukraine, Odessa "Synthesis of 5-Aryl-3-Acyloxy-7-Bromo-1,2-Dihydro-3H-1,4-Benzodiazepine- 2-ones, their Pharmaceutical Properties and Affinity for Central Benzodiazepine Receptors"
Investigation of self-assembling abilities of Cu(II), Cd(II) and Ni(II) complexes with 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin Sinelshchikova A.A. a , Enakieva Y.Y. a , Gorbunova Y.G. a , Nefedov S.E. b , Bessmertnykh-Lemeune A. c , Tsivadze A.Y. a , Guilard R. c a A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS b N.S. Kurnakov Institute of General & Inorganic Chemistry of RAS, Leninskiy pr.31, Moscow, 119991 Russia e-mail: asinelshchikova@gmail.com c Université de Bourgogne - ICMUB UMR CNRS 5260, 9 avenue Alain Savary - BP 47870, 21078 Dijon, France Earlier we have developed an efficient synthetic methodology toward meso- polyphosphoryl-substituted porphyrins and showed that self-assembling of Zn complex with 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin leads toward 2D coordination polymer in the solution as well as in the solid state 1,2 . Such self-assembling occurs due to formation of P=O…Zn bonds between adjacent porphyrin molecules. In the present work we studied interaction of other d-metals with 5,15- bis(diethoxyphosphoryl)-10,20-diphenylporphyrin and self-assembling properties of target compounds. Complexes of Cu(II), Cd(II) and Ni(II) were obtained by the reaction of corresponding acetate or acetylacetonate with free-base porphyrin. Complexes were characterized by UV-vis, IR, 1 H, 31 P NMR spectroscopy, MALDI-TOF MS analysis. Self-assembling abilities of complexes were studied by means of UV-vis, IR spectroscopy and X-ray monocrystal and powder diffraction. It was shown that cadmium and copper complexes demonstrate self-assembling in chloroform solution similar as zinc complex. In contrast nickel complex does not form supramolecular arrays in solutions. IR data confirm that in solid state self-assembling of cadmium complex occurs due to formation of coordination bonds P=O…Cd while nickel complex does not form such coordination bonds. The formation of 2D-coordination network in the case of Cu(II) and Cd(II) porphyrinates was also proved by means of X-ray diffraction analysis of mono- and polycrystalline complexes. At the same time Ni(II) porphyrinate crystalises without formation of P=O…M bonds. Acknowledgements: This work was performed in the framework of French-Russian Associated Laboratory “LAMREM” supported by ARCUS 2007 Burgundy-Russia project, Russian Foundation for Basic Research, the CNRS and Russian Academy of Sciences. REFERENCES 1. Enakieva Y.Y., Bessmertnykh A.G., Gorbunova Y.G., Stern C., Rousselin Y., Tsivadze A.Y., Guilard R. Org. Lett., 2009, 11, 3842-3845. 2. Kadish K.M., Chen P., Enakieva Y.Y., Nefedov S.E., Gorbunova Y.G., Tsivadze A.Y., Bessmertnykh-Lemeune A., Stern C., Guilard R. J. of Electroanalytical Chemistry, 2011, available online 08/02/2011, doi:10.1016/j.jelechem.2011.01.011.
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