ISMSC 2007 - Università degli Studi di Pavia

PSA 87
Luminescence of terbium and dysprosium complexes with p-sulfonatothiacalix[4]arene
in aqueous and surfactant media
Svetlana Kost a , Natalya Rusakova a , Asiya Mustafina b , Rustem Amirov c , Rustem Zairov c ,
Svetlana Solovieva b , Igor Antipin b , Alexander Konovalov b , Yuriy Korovin a
a A.V. Bogatsky Physico-Chemical Institute, 86 Lustdorfskaya doroga, 65080 Odessa, Ukraine
b A.E. Arbuzov Institute of Organic&Physical Chemistry, 8 Arbuzov str., 420088 Kazan, Russia
c Kazan State University, 18 Kremlevskaya str., 420008 Kazan, Russia
Molecular design of a sensing reagent capable of recognition the cations, anions, specific
analytes, pH, etc. is one of cardinal approaches to innovation of chemical analysis. It is wellknown
that calixarenes (cyclic products of phenol and formaldehyde condensation) are versatile
molecular scaffolds for design of highly efficient receptors, self-assembling systems such as
molecular capsules and well defined functional nanostructures. At the same time the chemistry
of the thiacalixarenes is very recent compared to the similar calixarenes that have been known
for over 20 years. Several papers have recently reported interesting progress in the field of the
chemistry and application of thiacalixarenes [1,2].
In this work we describe the 4f-luminescence behavior of the terbium and dysprosium watersoluble
complexes with p-sulfonatothiacalix[4]arene (TCAS) (Fig.) at room temperature in
aqueous and surfactant media.
SO 3 - Na +
S
- O
S
SO 3 - Na +
SO 3 - Na +
O -
Ln 3+
S
O -
S
OH
SO 3 - Na +
n H 2O, n =2-3
The spectral-luminescent characteristics of corresponding complexes are determined at the
presence of some neutral, anionic and cationic surfactants. It was determined that a change of
pH shows a highly sensitive influence on the luminescence of complexes with TCAS. Therefore
we considered the luminescent properties of the complexes with a view to the potential use in
sensor systems, in particular, for control of pH.
It has been shown that the presence of neutral and anionic surfactants have no influence on
luminescence intensity of complexes Tb(Dy)-TCAS. Presence of cationic surfactants in their
concentration is lower as compared to CMC (critical micelle concentration) results in formation
of associates with complexes due to an electrostatic attraction between SO3 - - groups of the
TCAS and molecules of cationic surfactants. These associates are characterized by more
intensive 4f-luminescence than complexes Tb(Dy)-TCAS in aqueous medium. The various
approaches to the increasing of the 4f-luminescence in these complexes are described and
discussed.
[1] N. Iki, S. Miyano, J. Incl. Phenom. Macrocycl. Chem., 2001, 41, 99-105.
[2] P. Lhotak, S. Shinkai, J. Phys. Org. Chem., 1997, 10, 273-282.
PSA 88
Photo-Responsive Structure of Supramolecular Polymers Constructed by a
Stilbene Cyclodextrin Dimer
Paul Kuad, Yoshinori Takashima, Hiroyasu Yamaguchi and Akira Harada
Department of Macromolecular Science, Graduate School of Science, Osaka University,
Toyonaka, Osaka 560-0043, Japan; e-mail: paul@chem.sci.osaka-u.ac.jp
Stilbene derivatives are expected to provide useful applications for optical switching, image
storage devices or molecular function regulation because their C-C double bond photoisomerisation
can induce
changes of various chemical and
physical properties. Previously,
we reported the formation of
supramolecular polymers based
on homo and hetero cyclodextrin
(CD) dimer and various ditopic
guests. [1]
In this work, we prepared
supramolecular polymer based
on β-CD dimer with functional
stilbene linker as new stimuliresponsive
systems and studied
its chemical and physical
properties. The guest dimer
consists of two adamantyl
groups linked by a pyridinium
derivative. We observed
interaction of the stilbene host
dimer with the guest dimer. The
Figure 1. Diffusion coefficient (D) of trans and cis stil-β-CD
dimer alone and C3 guest with trans and cis stil-β-CD dimer in
D2O at 30 ºC.
results indicate different complexation behaviour for the trans and cis form of the CD dimer.
ROESY NMR spectra of the mixture of host and guest showed correlation peaks between
adamantyl groups and inner protons of CDs for both isomers, indicating that the adamantyl
groups were included in the CD cavities. On the other hand, PFG NMR measurements,
Figure 1, reveal that the diffusion coefficient of the cis isomer complex was significantly lower
than that of the trans isomer at high concentration, indication the formation of a supramolecular
polymer with cis isomer whereas trans isomer forms smaller assemblies. Direct observation of
the different isomer mixture by AFM allows us to propose structures for the complexes
(Figure 2).
O
O
NH
N+
O
O
NH
N+
N +
O
N
O
N +
O
N
O
hυ
HN
O
NH
O
O
Figure 2. Proposed structures of 1/1 complex and supramolecular polymer.
N +
[1]. (a) Ohga K., Takashima Y., Takahashi H., Kawaguchi Y., Yamaguchi H., Harada A.,
Macromolecules, 2005, 38, 5897-5904. (b) Hasegawa Y., Miyauchi M., Y., Takashima Y.,
Yamaguchi H., Harada A., Macromolecules, 2005, 38, 3724-3730. (c) Takahashi H., Takashima
Y., Yamaguchi H., Harada A., J. Org. Chem., 2006, 38, 3724-3730.
N +
O
HN
O
NH
O
O
N +
N +
O
HN
O
NH
O