ISMSC 2007 - Università degli Studi di Pavia

PSB 59
Supramolecular mixed complexes of the crown-containing ditopic receptors
with organic acids and metal cation.
O.A. Fedorova, E.Yu. Chernikova, Yu.V. Fedorov, E.N. Gulakova,
M.M. Mashura, N.E. Shepel' and M.V. Alfimov
a Photochemistry Center of Russian Academy of Sciences, Novatorov str., 7a, Moscow, 117421,
Russia. E-mail: fedorova@photonics.ru
Compared to the large number of chromo/fluororeceptors for cations and anions, the
development of artificial receptors for organic acids is quite limited in spite of their importance
for biochemical analysis. In designing of the receptors which able to form multicomponent
molecular assemblies with ammonium cations, carboxylic and amino acids we used crowncontaining
hetarylphenylethenes possessing two binding centers of different nature. The main
interactions involved in its recognition are hydrogen bonding, metal cation binding and steric
complementary. In this work multicomponent molecular assemblies of crown-containing 15crown-5-ether
4-styrylpyridine (1) with potassium cations, phthalic and isophthalic acids in
MeCN were investigated by UV-VIS spectroscopy, ESI-mass, NMR and X-Ray analysis.
K +
H
O O
O
O
O
O O
O
O
O
O
O-
+ N
H + N
K +
O
O
O
O
N +
O
H O
O
MeO
H O
MeO
OH
O
O
OH
OH
O
N
N
N
O
O
O
O
O
O
O
O
K
O
O
O
O
O
O
O
+
K +
Hydrogen and coordination bonds as well as complementary of reacting molecules play the
important role in the assembly formation. The crown ether moiety prefers to bind with alkaline
and alkaline-earth metal cations, forming the 'sandwich' complex between 1 and large metal
cations like K + or Ba 2+ , resulting in hypsochromic shift of long wavelength absorption band of 1.
In the presence of phthalic acid the protonation of 1 was observed in MeCN solution
accompanying by bathochromic shift of long wavelength absorption band in UV-vis spectrum.
The addition of K + to acid complex results in the formation of the mixed sandwich complex. In
case of isophthalic acid a more complicated complex containing two isophthalic acids, three
ligands and three K + was found. In this complex isophthalic acid interacts with pyridine residue
by hydrogen bond formation, crown ether fragments are connected to each other by potassium
cations.
Acknowledgment. The study was supported by CRDF (Grant RUC2-2656-MO-05), INTAS
(Grant 03-51-4696), RFBR (Projects Nos. 05-03-32268 and 06-03-32899).
PSB 60
New Series of 18-Membered Aza-oxa-thia and Coumarin Pendent Armed
Macrocyclic Systems, Synthesis and Applications
Abbas Shockravi * , Hasan Valizadeh, Hamideh Hoseini and Zahra Taheri
Tarbiat Moallem University, 49-Mofatteh Ave. Faculty of Chemistry, Post Code 15416, Tehran,
Iran. Abbas_Shockravi@yahoo.co.uk; Shockravi@tmu.ac.ir
In the course of the search for new prospective Aza-oxa-thia macrocyclic compounds we
found that the reaction of different diamines and diacid chlorides/diesters leads to 12- to 20-
membered (i.e. 1,2) macrocycles and 24- to 40-membered due to dimerization processes [1,2].
Conductometry studies of macrocycle (1) and NMR studies of the stiochiomertry and stabilities
of macrocycle (2) with Ba +2 , Sr +2 , Hg +2 , K + , Ag + and Tl + ions in binary 50% acetonitrilenitrobenzene
mixture at 300 K proved that macrocycle (1) acts as Ag + sensor and the stabilities
of the resulting 1:1 complexes vary in the order Ba 2+ > Sr 2+ > Hg 2+ ,… with macrocycle (2).
Studies on the macrocycle (1) and its sulfoxide derivative revealed that they were biologically
active and cytotoxic via oxidative response triggering as studied by V79 cell line [3]. Syntheses
of several chromogenic macrocycles derived from (1) involve the fluorescence species such as
coumarin subunit attached to nitrogen atom (3, 4). The chemosensor activities of these novel
coumarin lariat ether macrocycles are under study in our research laboratory and the results will
be presented in the meeting.
N
H
O NH
HN
O
O
S
O
(1)
O
H
N
O
O
S
O
NH HN
O O
O
(2)
R=a-c
H
N
O NH
HN
O
O O
O O O
Br
O
O
O
O
(a) (b) (c)
O
S
R
N
O
(3)
H
N
O NH
HN
O
[1]. A. Shockravi, S. Bavili T, E. Rostami, A. Yousefi, A. Dejurian and R. Tohidi, J. Inclusion
Phenom. Macrocyclic Chem., 2004, 49, 163-166.
[2]. A. Shockravi and S. Bavili T, J. Inclusion Phenom. Macrocyclic Chem., 2005, 52, 223-227.
[3]. M. Mashhadi Akbar Boojar and A. Shockravi, Bioorganic and Medicinal Chemistry., 2007,
18, 3337-3344.
O
R
N
S
O
(4)