4th EucheMs chemistry congress

wednesday, 29-Aug 2012
s798
chem. Listy 106, s587–s1425 (2012)
organic Chemistry, Polymers – ii
supramolecular Chemistry – iii
o - 3 8 7
AzoBenzene MACroCyCLiC ChiroPtiCAL
SwitCheS
M. PutALA 1 , A. KiCKová 1 , r. MiSiCáK 1
1 Comenius University in Bratislava, Department of Organic
Chemistry Faculty of Natural Sciences, Bratislava, Slovak
Republic
Light-driven molecular machines have attracted intensive
attention for their potential applications in the field of optical data
processing and storage. One of the alternative strategies for the
non-destructive readout is represented by utilization of their
chiroptical properties. Photochromic diaryldiazene unit undergoes
significant change in molecular geometry upon trans-cis
isomerization which has been successfully explored for
construction of chiroptical switches in combination with
binaphthalene moiety as conformation sensitive chiral unit
(changing dihedral angle between naphthyl units).
Our results on the synthesis and characterization of
macrocyclic switches consisting of photochromic diazene and
binaphthalene chiral moiety attached via suitable linkers will be
reported. In comparison to the previously reported analogues with
more flexible propan-1,3-diyldioxy linkers, the derivatives with
more rigid acrylamide and urea linkers exhibit advanced
switching performance: switching of CD signal intensity up to 1:3
for compound with acrylamide linker, or even switching the signal
sign for compoud with urea linker.
Keywords: azo compounds; binaphthyl derivatives; chiroptical
switches;
supramolecular Chemistry – iii
4 th EucheMs chemistry congress
o - 3 8 8
SeLf-ASSeMBLed ttf-BASed redox-ACtive
reCePtorS: froM 2d PoLyGonS to 3d CAGeS
S. BivAud 1 , S. GoeB 1 , J. y. BALAndier 1 , M. ChAS 1 ,
M. SALLe 1
1 MOLTECH-Anjou, UFR Sciences, Angers, France
The methodology of self-assembly driven by metals
(typically Pt, Pd) allowed the preparation of a large number of
molecular polygons (triangle, square,...) and polyhedrons (cubes,
prisms, …) presenting remarkable properties. [1] For instance, the
water-soluble cage described below by Fujita et al showed
surprising catalytic activities. [2]
Nevertheless, very few electro-active polygons or
polyhedrons have been described, and none presents an
electron-rich cavity. In this context, we have initiated a project to
elaborate new self-assembled discrete structures incorporating
redox-active walls based on tetrathiafulvalene (TTF). [3]
We recently described the first self-assembled molecular
square and triangle integrating TTFs units, reversibly oxidizable
and able to complex the electron-poor fullerenes C or C . 60 70 4
In this communication, we will focus on our last results in
this area, and in particular on several new three dimensional
capsules based on TTF, bispyrrolo-TTF (BPTTF) and
extended-TTF (exTTF) based-ligands (see below), and on their
capability to bind electro-deficient units.
references:
1. R. Chakrabarty, P. S. Mukherjee, P. J. Stang, Chem. Rev.
2011, 111, 6810-6918.
2. a) S. Horiuchi, Y. Nishioka, T. Murase, M. Fujita, Chem.
Commun. 2010, 46, 3460-3462 ;
b) T. Murase, S. Horiuchi, M. Fujita, J. Am. Chem. Soc.
2010, 132, 2866-2867.
3. D. Canevet, M. Sallé, G. Zhang, D. Zhang, D. Zhu, Chem.
Commun. 2009, 2245-2269.
4. a) J. Y. Balandier, M. Chas, P. Dron, S. Goeb, D. Canevet,
A. Belyasmine, M. Allain, M. Sallé, J. Org. Chem.
2010, 75, 1589 ;
b) J. Y. Balandier, M. Chas, S. Goeb, P. I. Dron, D. Rondeau,
A. Belyasmine, N. Gallego, M. Sallé, New J. Chem.
2011, 35, 165 ;
c) S. Goeb, S. Bivaud, J. Y. Balandier, P. I. Dron, M. Chas,
M. Sallé, Chem. Commun. 2012, 48, 3106-3108.
Keywords: Sulfur heterocycles; Self-assembly; Supramolecular
chemistry; Molecular recognition;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc