ISMSC 2007 - Università degli Studi di Pavia

Azomacrocyclic derivatives of pyrrole as chromoiononophores and
fluoroionophores
Ewa Wagner-Wysiecka, Elbieta Luboch, and Tomasz Rzymowski
Chemical Faculty, Gdansk University of Technology, Narutowicza St 11/12, 80-952 Gdask,
Poland
Crown ethers incorporating an azo group as a part of macrocycle are interesting metal
complexing agents showing properties typical for azo metallochromic reagents [1]. Recently, we
described series of chromogenic crown ethers bearing simultaneously heterocyclic residue of
pyrrole [2] or imidazole [3] as a part of macrocycle. This work presents synthesis and properties
of novel pyrrole containing chromogenic crown ethers (Fig. 1) and studies of metal ion
complexation. The complexation was investigated with the use of UV-Vis and fluorescence
spectroscopy.
O
O
O
O
N
N
H
N N N
O
O O
O
N N
H
N N N
O
O
O
O
N
N
H
N N N
Fig.1 Investigated azomacrocyclic derivatives of pyrrole
N O O
S
S
O
O
N
O
N
N
H
N N N
O
S
O
N
O
N
N
H
N N N
Complexation of alkali, alkaline earth and heavy metal cations (Pb 2+ , Co 2+ , Ni 2+ , Zn 2+ ) was
studied in different organic and water containing solvent systems.
[1]. For example see review: E. Luboch, R. Bilewicz, M. Kowalczyk, E. Wagner-Wysiecka, J.F.
Biernat, Azo Macrocyclic Compounds. In G. W. Gokel , Ed.,Advances in Supramolecular
Chemistry; Cerberus: South Miami, USA, 2003, vol.9, p.72.
[2]. E. Luboch, E.Wagner-Wysiecka, M.Fainerman-Melnikova, L.F.Lindoy, J. F Biernat,
Supramol. Chem. 2006, 18, 593-601.
[3]. E.Wagner-Wysiecka, M. Jamrógiewicz, J. F. Biernat, Tetrahedron, 2007, 63, 4414-4421.
Financial support from the Polish State Committee for Scientific Research, Grant no.
3TO9A15127 is kindly acknowledged.
PSB 79
PSB 80
Cation and anion binding studies of a large N,O-donor macrocycle:Single
ion extraction and synergistic enhancement
Marco Wenzel 1,2 , Kerstin Gloe 1 , Karsten Gloe 1 , Gert Bernhard 2 , Jack K. Clegg 3 , Xue-K. Ji 3 ,
Leonard F. Lindoy 3
1 Department of Inorganic Chemistry, TU Dresden,01062 Dresden, Germany
2 Institute of Radiochemistry, Research Centre Dresden-Rossendorf, 01314 Dresden, Germany
3 School of Chemistry, University of Sydney, NSW, 2006, Australia
Mixed N,O-donor macrocycles have been shown to result in interesting complexation properties
towards both cations and anions (the latter on protonation of the macrocycle's nitrogen
functions).[1-3]
In the present study the phase transfer properties of 1 toward selected transition metal ions and
anions have been evaluated by liquid-liquid extraction studies under different pH conditions.
The order of increasing extraction follows the Irving-Williams series Co(II) < Ni(II) < Cu(II) >
Zn(II), while the anion extraction is contolled by the Hofmeister series.
A synergistic enhancement of metal extraction was obtained on exploiting a dual host strategy
[4] in which the tripodal thiourea host 2 was incorporated in the system. In this case atypical
anti-Hofmeister behaviour was obtained in which significant metal extraction of chloride or
sulfate was observed from solution.
N
O
O
NH
NH
HN
HN
O
O
N
S
NH
S
NH
1 2
[1] N.A. Bailey, D. E. Fenton, S.J. Kitchen, T.H. Lilley, M.G. Williams, P.A. Tasker, A.J. Leong
and L.F. Lindoy, J. Chem. Soc. Dalton Trans., 1991, 627-637.
[2] H. Adams, N.A. Bailey, D.E. Fenton, I.G. Ford, S.J. Kitchen, M.G. Williams, P.A. Tasker, A.J.
Leong and L.F. Lindoy, J. Chem. Soc. Dalton Trans., 1991,1665-1674.
[3] L. Tušek-Boži, š, Polyhedron 24, 2005, 97–111.
[4] K. Kavallieratos, R.A. Sachleben, G.J. Van Berkel and B.A. Moyer, Chem. Commun., 2000,
187-188.
N
NH
NH
HN
NH
S