XII Iberian Meeting of Electrochemistry XVI Meeting of the ...

XII Iberian Meeting of Electrochemistry & XVI Meeting of the Portuguese Electrochemical Society PL 05
Electrochemistry of molecules with two (or more) redox
centers
J. Heyrovský Institute of Physical ChemistryCzech Rep.
jiri.ludvik@ jh-inst.cas.cz
Molecules of organic or coordination compounds have often two or more redox centers.
These centers may be independent or communicating, according to their mutual distance
and extent of electron delocalization between them. The most attractive is the case of
strong interaction between the centers, when the redox active groups do not preserve
their typical redox properties and create a new electron system with its specific redox
reactivity. To understand the structural rules and eventually to tune the redox properties
is an interesting theme for fundamental research as well as for development of catalysts,
dyes, pharmaceutical products, agrochemicals etc.
Electrochemical approach is a very suitable experimental tool for examination of such
intramolecular electron interactions. In the contribution, several examples will be
mentioned: azines, where the N-N bond prevents the electron interaction of two C=N
double bonds [1], mono-oximes of aromatic 1,2-diketones, where two isomers have
different reduction behaviour [2]. Next examples are represented by Fischer
aminocarbene complexes [3-4] and by various mono-and dinuclear transition metal
complexes bearing ferrocene as 1) another redox center able to form a new delocalized
system [5-8], 2) as an electrochemical probe [9-10]. Finally, the recent investigation of
redox properties of two types of polynitrocompounds (geminal dinitroderivatives and
mono-, di-, tri- and tetranitrocalixarenes) will be discussed.
Acknowledgments: The work was supported by the grants IAA 400 400 813 (Grant Agency of the
Academy of Sciences of the Czech Republic) and ME 09 002 (Ministry of education, youth and
sports of the Czech Republic).
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[2] Celik, H.; Ludvík, J.; Zuman, P. Electrochemistry Communnication, 2006, 8, 1749.
[3] Meca, L.; D.; Ludvík, J.; I.; , P. Organometallics, 2004, 23, 2541.
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Acta, 2005, 50, 4911.
[5] Organometallics, 1996, 15, 543.
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[7] Auzias, M.; Süss-J. Inorg. Chim. Acta, 2007, 360, 2023.
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September, 811, 2010. ISEL - Lisbon 16