ISMSC 2007 - Università degli Studi di Pavia

Macrocyclic Porphyrin-Bidentate Chelate Conjugates
Jonathan A. Faiz, Fabien Durola and Jean-Pierre Sauvage.
Laboratoire de Chimie Organo-Minérale, Université Louis Pasteur, Institut de Chimie, 4 rue
Blaise Pascal, 67070 Strasbourg, France.
The synthesis of macrocycles that contain both porphyrin and chelating units is an interesting
challenge for in the construction of molecular machines that utilise the coordination properties of
both the chelate and the metallated porphyrin. We have developed a direct approach using
commercially available tetrakis(4-hydroxyphenyl) porphyrin as a starting material. Statistical
cyclisation reactions with either phenanthroline or biisoquinoline [1,2] units have led to the
macrocycles I and II. It has been shown that careful choice of the chelating unit and the chain
length can lead to the preferential formation of the cis or trans isomers of the porphyrin
macrocycle. Alkylation of the remaining phenol groups with a THP-masked alcohol provides a
site for deprotection and subsequent functionalisation to create double macrocycles capable of
simultaneously threading two axles. This provides a complementary approach to the synthesis
of double macrocycles [3] and 4-rotaxanes [4] already investigated by us.
THPO
O
O
N
O O
N
N
H
H
N
I
N
N
O
O
OTHP
[1] L. Flamingni, A.M. Talarico, J.-C. Chambron, V. Heitz, M. Linke, N. Fujita and J.-P. Sauvage,
Chem. Eur. J., 2004, 10, 2689-2699 and references therein.
[2] F. Durola, D. Hanss, P. Roesel, J-P. Sauvage and O.S. Wenger, Eur. J.Org. Chem., 2007,
125-135.
[3] J. Frey, T. Kraus, V. Heitz and J-P. Sauvage, Chem. Commun., 2005, 42, 5310-5312.
[4] Collin, J. Frey, V. Heitz, E. Sakellariou, J-P. Sauvage and C. Tock, New. J. Chem., 2006, 10,
1386-1389.
O
O
N
O
OTHP
O
O
N
NH N
N HN
THPO
II
O
PSA 49
O
O
PSA 50
Supramolecular assemblies of heterostylbene molecules: structure and
properties
O. A. Fedorova, a Yu. V. Fedorov, a N. E. Shepel, a E. N. Gulakova, a M. M. Mashura, a
G. Jounauskauskas b .
a
A.N.Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
Vavilova str., 28, GSP-1, Moscow, 119991, Russia; fedorova@photonics.ru
b
Centre de Physique Moléculaire Optique et Hertzienne – UMR CNRS 5798, University
Bordeaux, France
Aggregates of organic dyes have been extensively studied and reported in the literature
because of their application in many fields of science, such as photographic process, organic
photoconductors, photo-assisted process in biological systems, a prominent nonlinear optics
materials. Molecular self-association of dyes is a well-known phenomenon, occurring in
concentrated solution of dyes or induced by its preferential adsorption onto a wide variety of
substrates, such as solids and microheterogeneous media. In the report the associate formation
of the crown-containing hetarylphenylethenes assembled due to combination of coordination
bonds, hydrogen bonds and stacking interaction was analyzed. The principals of the
construction of the aggregates of the determined architecture were suggested.
O O
O
O
O
O O
O O
O
O O
O
O
O
N
N
N +
N+
O
O
O
O O
N
N
O
O
N
-
OH
O
O
N
OH
OH
N
O
O
O
O
O
O
O
O
O
O
O
O O
O
O
O
O O
O
O
O
O O
O O
O
O O
O
O
O
O O
O O
O
O O
O
O
N +
N +
O
O
N N
N N
N N
O O
O
The formation of the assemblies is observed by the change in the electronic absorption
and emission spectra, since they have different photophysical properties when compared with
the dye monomer. The formation of these aggregates is strongly dependent of several factors,
like dye molecular structure, nature of metal cations and presence of organic acids. It was found
that photochemical transformations of the assemblies of dyes substantially differ from those of
initial dye monomer.
Acknowledgment. The study was supported by CRDF (Grant RUC2-2656-MO-05), INTAS (Grant
03-51-4696), RFBR (Projects No. 06-03-32899 and 05-03-32268).
O O
O
O O
O
O
O
O
O
N+
N+
O
O O
O
O
O
O
O O
O
O
O
O
O
O
O
O
O
O
O
O