International Summer School PROGRAM - Laboratoire d'Infochimie ...

Synthesis and investigation of complexing, optical and electrochemical activities of
crown-containing oligothiophene derivatives
Artemiy Mizerev a , Elena Lukovskaya a , Olga Fedorova a , Yury Fedorov b , Alla Bobylyova a , Anna
Moiseeva a , Aleksander Anisimov a
a
Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory, 119992 Moscow,
Russia, E-mail: lukov@petrol.chem.msu.ru; Fax: +7 (495) 932 85 68
b
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova
str., 119991, Moscow, Russia
Functional oligothiophenes have attracted comprehensive interest among researchers all over the
world and have actually been advanced to be among the most frequently used π-conjugated materials, in
particular as active components in organic electronic devices and molecular electronics.
Thiophene-containing donor-acceptor substituted systems show electron and energy transfer
processes. The changes in physical properties (e.g., absorption, fuorescence, electrochemistry, etc.) of
these derivatives strongly depended on the nature of both the π-conjugation and the type of donor-
acceptor substitution. We introduced in conjugated system thiophene carrying 15-crown-5-ether ring
directly linked to the 3- and 4-positions of the thiophene ring (1) or benzo-15-crown-5-ether (2) as a
donor and pyridine residue as an acceptor.
Fe +2 , Cd +2
N
electrochemical response
S
S
optical response
O
O
O
O
O
Mg +2 , Ca +2 , Ba +2
Presented molecules contains two centres of coordination: crown-ether and pyridin fragments. It is
known that 15-crown-5-ether in the solution of acetonitrile forms strong complexes with cations of
alkaline earth metals. Cations of heavy metals coordinate pyridin fragment with a formation of complex
compounds. Coordination of cations with crown-ether fragment causes hypsochromic shift of absorbance
spectra, but optical response is low. Coordination with pyridine fragment causes bathochromic shift. In
this case the response is remarkable.
Electrochemical activity of the complexes corresponds with the optical ones. Complex compounds
with crown-ether are electrochemical inactive and there is a notable response in case of pyridin fragment.
Acknowledgments to RFBR program (09-03-00550).