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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.