ISMSC 2007 - Università degli Studi di Pavia

PSA 77
Synthesis and molecular recognition studies of new enantiopure BODIPY
linked monoaza-18-crown-6 ligands
Ildikó Móczár a , Péter Huszthy a,b , Mihály Kádár c , Klára Tóth c
a Department of Organic Chemistry and Technology, Budapest University of Technology and
Economics, H-1111 Budapest, Szent Gellért tér 4, Hungary
b Research Group for Alkaloid Chemistry of the Hungarian Academy of Sciences
H-1111 Budapest, Szent Gellért tér 4, Hungary
c Department of Inorganic and Analytical Chemistry and Research Group for Technical
Analytical Chemistry of the Hungarian Academy of Sciences, Budapest University of
Technology and Economics, H-1111 Budapest, Szent Gellért tér 4, Hungary
The use of fluorescent sensor molecules for the detection of metal ions, organic and biological
analytes has attracted much research interest from synthetic point of view as well as from the
point of view of understanding the photophysical mechanisms governing the spectroscopic
behaviour of such systems [1, 2]. Among others BODIPY dyes are used as fluorescent
signalling moiety of sensor molecules because of their advantageous spectroscopic properties.
R
*
O
O
N
O
R=H, alkyl
Figure
N
N
B F
F
OMe
O
O
*
R
According to the literature [3] BODIPY linked
monoaza-18-crown-6 ether (Figure, R=H) is
a K + and Ca 2+ selective fluorescent ICT
(internal charge transfer) type sensor
molecule and provides information about the
complexation via spectral shifts of the
absorption and emission bands with
enhancement of the fluorescence intensity.
Based on the advantageous properties of
the above mentioned crown ether (Figure,
R=H), we synthesized its enantiopure
analogues (Figure, R=alkyl) bearing two
alkyl groups on their chiral centers. The
complexation of the BODIPY linked ligands
(Figure, R=H and alkyl) with the
enantiomers of chiral primary ammonium
salts and also metal ions have been studied
by UV-Vis and fluorescence spectroscopies.
Financial support of the National Scientific Research Fund of Hungary (OTKA: K 62654, T
46403) is gratefully acknowledged.
[1] Handbook of Photochemistry and Photobiology, ed. by H. S. Nalwa, Volume 3:
Supramolecular Photochemistry, Chapter 5,6, American Scientific Publishers, Stevenson
Ranch, California, USA, 2003
[2] J. F. Callan, A. P. de Silva and D. C. Magri, Tetrahedron, 2005, 61, 8551-8588
[3] M. Baruah, W. Qin, R. A. L. Vallée, D. Beljonne, T. Rohand, W. Dehaen and N. Boens,
Organic Letters, 2005, 7, 4377-4380
PSA 78
Copper(I) Complexes with Reversibly-Formed Imine Bonds : Synthetic
Control via Self-Assembly
Marie Hutin a , Gérald Bernardinelli b , Jonathan R. Nitschke a
a Sciences II, University of Geneva, 30 quai Ernest Ansermet, 1211 Geneva 4, Switzerland.
b Laboratory of X-Ray crystallography, University of Geneva, 24 quai Ernest Ansermet, 1211
Geneva 4, Switzerland.
Our group has developed a self-assembly methodology that allows unusual structures to be
created in excellent yield. Amine and aldehyde subcomponents are held together by reversiblyformed
imine (C=N) bonds that self-assemble around copper(I) templates.
The reaction of aldehyde A with diamine B and copper(I) in aqueous solution gave the single
macrocyclic structure 1. X-ray crystallography confirmed the presence of this structure in the
solid state. The addition of sulfanilic acid (4 equiv) to an aqueous solution of macrocycle 1
resulted in its conversion to helicate 2. By changing the pH, it was thus possible to switch
dynamically between the open topology of a helicate and the closed topology of a
macrocycle.[1]
HN
H
N
O O O O
NH HN
N N
N N
Cu Cu
N N
N N
O O
3
H
N
H
N
NH2 2
C
NH 2
2
A
N
N
O
O
2 Cu(I)
O
2
B
O
NH2 NH2 N N
N Cu N
N Cu N
N N
When dianiline C was employed instead of diamine B as a subcomponent, a single product was
observed by NMR spectroscopy. Based upon the length and flexibility of the diamine spacer, we
were able to select catenate 3 as the unique product of this self-assembly reaction.[1]
The
reaction of diformylpyridine and copper(I)
with diamine B or 8-aminoquinoline in
acetonitrile solution generated
“undersaturated” macrocycle 4 (only three
nitrogen donors per copper) or
“oversaturated” helicate 5 (five such donors),
respectively. When diamine B,
diformylpyridine and 8-aminoquinoline are
present simultaneously, the possibility exists
N N
Cu
N N
Cu
N N
O O
N N
Cu
N N
N
N N
Cu
N N
N
Cu
N N
N N
Cu
N N
of creating a heterocomplex in which both copper(I)
ions and ligands are valence-satisfied
(complex 6). This complex could also be prepared through mixing macrocycle 4 and helicate 5
together in acetonitrile solution.[2]
N
O O
4 5
2
O O
6
[1]
M. Hutin, C.A. Schalley, G. Bernardinelli, J.R. Nitschke, Chem. Eur. J., 2006, 12, 4069-4076.
[2] M. Hutin, G. Bernardinelli, J.R. Nitschke, Proc. Natl. Acad. Sci. USA, 2006, 103, 17655-
17660.
O
O
O O
1
4 H 3N SO 3 -
+
2 O
O -O3S H3N NH3 2 O
H 2N
+
+
NH2
O
4 H 2N SO 3 -
N N
N Cu N
N Cu N
N N
SO 3 -
-O3S -
2 SO3