ISMSC 2007 - Università degli Studi di Pavia

Novel ditopic probes for different metal cation recognition
Elena Tulyakova a , Olga Fedorova b , Yuri Fedorov b , Gediminas Jonusauskas c , Alexander
Anisimov a
a Chemistry Department, M. V. Lomonosov Moscow State University, 119992, Moscow, Russia
b Photochemistry Center of Russian Academia of Sciences, 119421 Moscow, Russia
CPMOH – UMR CNRS 5798, Bordeaux University I, 33405 Talence, France
Design of new probes for cooperative recognition of hard and transition metal cations along with
alkaline earth metals is topic of current importance in medicine and environmental monitoring.
The aim of present work is investigation a bifunctional molecules combined two different
receptor residues which show such a multifold signal expression in the presence or absence of
one or two different types of metal cations. New ion-selective receptors with two ionophoric
centers had been obtained due to the ability of benzocrown ether moiety to bind alkali, alkaline,
earth metal cations and the affinity of phenylazathiacrown ether to heavy metal cations. The
response of compounds is useful both in absorption and emission spectroscopy: the strong
wavelength shifts observed in the presence of cations make the dyes suitable for dual
wavelength analysis in self-calibrating measurements. The interaction strength between ligands
and cations was measured. Due to simple model of complex formation the reliable correlation
between the concentration of metal cations in solution and value of optical response of dyes 1-4
can be obtained. So compounds can be considered as probe designed with the purpose to
measure cation concentration in different kind of cationic analysis.
R 1 =
R 1
O
O
1 : 2 : R1 N R2 N
R2 - CH3 -
ClO
ClO4 CH 4
3
O
O
O
= Mg
R2 =
2+ , Ba2+ , Ca2+ = Hg2+ , Cu2+ , Ag +
S O
N
S O
3 : R1 N (CH2) 3 N R2 4 : R1 N (CH2) 3 N S
- ClO4 - ClO4 - ClO - R2 4 ClO4
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Acknowledgements. Generous financial support from the Russian Science Support Foundation,
grant supporting for talented students, PhD students and young scientists of M.V. Lomonosov
Moscow State University and RFBR (05-03-32268, 06-03-32899) are gratefully acknowledged.
Preparation of new octa(alkoxy) pyrazinoporphyrazines
Rabia Zeynep Uslu Kobak, Ahmet Gül
Technical University of Istanbul, Department of Chemistry, 34469, Istanbul, Turkey,
Fax:(+90) 212 285 63 86, e-mail: uslur@itu.edu.tr
Substituted azaphthalocyanines(AzaPc’s) are generally more soluble than the corresponding
phthalocyanines (Pc’s) and may, therefore, be more applicable in various areas of technology
and especially in photodynamic therapy. A limited number of substituted AzaPc’s have been
reported in the literature, where alkyl groups, carboxylic acids or esters are mentioned as
substituents. For instance, AzaPc’s , substituted with carboxylic acids, were prepared as
potential activators for photodynamic cancer therapy[1].
Presently we report the synthesis of a new alkoxy substituted pyrazine dicarbonitrile and its
cyclotetramerisation to AzaPc. The metal complexes were synthesized by template
cyclotetramerisation of the pyrazinedicarbonitrile in the presence of the appropriate metal salts.
The new ligand and AzaPc’s were characterized by UV-Vis, IR, 1 H-NMR and mass spectra[2,3].
O 2N
O 2N
O
O
O 2N
O 2N NO 2
N
N
N
N
N
O O
N N
N
O
N
M
N
N
O
N
N
N
M=Zn,Co,Cu
References
[1] Morkved H.E., Ossletten H., Ksojen H., Acta Chemica Scandinavica , 1999, 53, 1117-1121.
[2] Uslu R.Z., Gül A., C.R. Acad. Sci. Paris. Serie IIC/Chimie , 2000 ,643-648.
[3] Nazlı A.,Gonca E., Gül A., Journal of Porphyrins and Phthalocyanines,2006,10, 996-1002.
N
N
NO 2
O
O
NO2
NO 2
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