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The features of the coordination networks formation of meso-mono-
and di-phosphorylated zinc porphyrins
Yu.Yu. Enakieva a,b , Yu.G. Gorbunova a,b , A. Bessmertnykh c , S.E. Nefedov b , C. Stern c ,
A.Yu. Tsivadze a,b and R.Guilard c
a A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS, Moscow
b N.S. Kurnakov Institute of General and Inorganic Chemistry of RAS, Moscow
c
Universite de Bourgogne ICMUB UMR CNRS 5260, 9 avenue Alain Savary, 21078
Phosphorylated porphyrins are promising models for elaboration of highly
ordered supramolecular systems of various architectures due to features of P=O-groups
and number, nature and arrangement of other peripheral functional groups of porphyrin.
N
X
N N
`Y Zn
X
Previously we have developed a general method to prepare new phosphoryl-
N
Y
Y=Y`= PO(OEt) 2, X= C6H5 (1a) ; Y`= H (2a)
Y=Y`= PO(OEt) 2, X= C6H5CN (1b) ; Y`= H (2b)
Y=Y`= PO(OEt) 2, X= C6H5CH3 (1c) ; Y`= H (2c)
Y=Y`= PO(OEt) 2, X= C6H5OCH3 (1d) ; Y`= H (2d)
Y=Y`= PO(OEt) 2, X= C6H5COOCH3 (1e) ; Y`= H (2e)
studied by means of X-Ray diffraction analysis.
substituted porphyrin receptors (1a-
e, 2a-e). The optimal conditions of
crystal growth for these compounds
were found and its structures were
It was shown [1] that the self-assembly of 1а leads to the formation of 2D
coordination network. Introduction of linear CN-group (1b) doesn`t change the
architecture of final network. However, when bulky electron-donating CH3-group
is
introduced (1c), dramatic changes of crystal structure occur leading to the formation of
pseudo-3D assembly constructed from alternating molecules, containing zinc ions with
coordination numbers equal to 5 and 6. Analogous self-assembling architecture was
observed for the complex 1d. Further increasing of the bulkiness of the phenyl-group
substitutes in 1e leads to even more sophisticated structure.
It should be note that the self-assembling of mono-phosphorylated porphyrins
(2a-e) also depends on the nature of peripheral substituent. Thus, the complex 2a forms
1D linear polymer, while the complex 2b forms dimers where the phosphoryl-group of
one molecule binds to the zinc ion of the other one. Self-assembling of complexes 2c-e
leads toward “calyxarene-like” structure including 4 zinc-porphyrinato-units.
Acknowledgements: This work was performed in the framework of French-Russian Associated
Laboratory “LAMREM” and “SUPRACHEM”, supported by ARCUS 2007 Burgundy-Russia project,
Russian Foundation for Basic Research, the CNRS and Russian Academy of Sciences.
[1] Enakieva Y.Y., Bessmertnykh A.G., Gorbunova Y.G., et. al. Org. Lett., 2009, 11, 3842-3845.