Supramolecular Chemistry for Nanosciences
Supramolecular Chemistry for Nanosciences
Supramolecular Chemistry for Nanosciences
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<strong>Supramolecular</strong> <strong>Chemistry</strong><br />
<strong>for</strong> <strong>Nanosciences</strong><br />
Guy Royal & L. P. Lévy<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
1
<strong>Supramolecular</strong> chemistry<br />
1987<br />
Nobel prize to:<br />
Donald J. Cram<br />
Jean-Marie Lehn<br />
Charles J. Pedersen<br />
Jean-Marie Lehn<br />
For their development<br />
of the field of<br />
supramolecular<br />
chemistry<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
2
Fundamentals of <strong>Supramolecular</strong> chemistry<br />
● Host-Guest<br />
chemistry<br />
+<br />
Selective<br />
Host-Guest complex<br />
(Supramolecule)<br />
molecular<br />
recognition<br />
Host molecule<br />
(Receptor)<br />
Guest molecules<br />
(Substrate)<br />
● Hydrogen bonding<br />
● π−π Stacking interactions<br />
● Electrostactic interactions (ion-ion, ion-dipole, dipole-dipole)<br />
● Van der Walls <strong>for</strong>ces<br />
● Hydrophobic/solvatophobic interactions<br />
● Coordination bonds (Metal-donor bonds)<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
Non-Covalent interactions<br />
are involved<br />
3
Fundaments of <strong>Supramolecular</strong> chemistry<br />
● Host-Guest<br />
chemistry<br />
+<br />
Selective<br />
Host-Guest complex<br />
(Supramolecule)<br />
molecular<br />
recognition<br />
Host molecule<br />
(Receptor)<br />
Guest molecules<br />
(Substrate)<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
K +<br />
O<br />
O<br />
K +<br />
O<br />
O<br />
O<br />
O<br />
[18]Crown-6<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
4
Fundaments of <strong>Supramolecular</strong> chemistry<br />
● Host-Guest<br />
chemistry<br />
Host-Guest complex<br />
(Supramolecule)<br />
Host molecule<br />
(Receptor)<br />
+<br />
Guest molecules<br />
(Substrate)<br />
Selective<br />
Reversibility<br />
molecular<br />
recognition<br />
● Reversibility:<br />
- The thermodynamic equilibrium can be reached<br />
- Dynamic architectures<br />
- Change in constitution, shape, properties…<br />
- Capacity of error correction (not available <strong>for</strong> fully covalent systems)<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
5
Bottom-up Fabrication<br />
design +<br />
synthesis<br />
Molecular<br />
Components<br />
self-assembly,<br />
self-organization<br />
FUNCTION<br />
Shape, size, properties<br />
(chemical, photochemical,<br />
redox, …)<br />
<strong>Supramolecular</strong><br />
System<br />
Integration into device /<br />
connexion to macroscopic world...<br />
Nanomaterial<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
6
design +<br />
synthesis<br />
What kind of molecules ?<br />
Molecular<br />
Components<br />
Fe<br />
N N<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
N<br />
N<br />
HS<br />
R<br />
"Building blocks":<br />
- Complexing molecules<br />
- Redox units<br />
- Photosensitive molecules<br />
- Conjugated or saturated molecules<br />
- Carbon nanotubes, fullerenes…<br />
- Molecules that can be attached onto a surface<br />
- …<br />
From very simple to very complex…<br />
Only limited by imagination and… organic synthesis!!!<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
7
design +<br />
synthesis<br />
What kind of molecules ?<br />
Molecular<br />
Components<br />
Light absorbed<br />
O<br />
O<br />
N<br />
O<br />
O<br />
O<br />
No Light emitted<br />
N N<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
R<br />
Self<br />
assembly<br />
K +<br />
Photochemical<br />
sensing and detection<br />
Fe<br />
N<br />
N<br />
HS<br />
Light absorbed<br />
O<br />
O<br />
N<br />
K +<br />
O<br />
O<br />
O<br />
A. P. De Silva, S. A. De Silva,<br />
J. Chem. Soc, Chem.<br />
Commun., 1986, 1709<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
Light emitted<br />
8
Self-assembly<br />
of molecular components<br />
N<br />
N<br />
Zn<br />
N<br />
N<br />
Fe<br />
design +<br />
synthesis<br />
N<br />
N<br />
Zn<br />
N<br />
N<br />
self-assembly<br />
NHR<br />
Fe<br />
R<br />
NH<br />
R<br />
Fe<br />
N<br />
R<br />
N<br />
N<br />
HNR'<br />
Zn<br />
N<br />
R<br />
N<br />
N<br />
Zn<br />
R'NH<br />
N<br />
N<br />
R<br />
Fe<br />
<strong>Supramolecular</strong> structure<br />
(dimer)<br />
R<br />
G<br />
Guest species<br />
(neutral molecule)<br />
Application: electrochemical detection of guest molecules<br />
04/03/2008 C. Bucher, M1-<strong>Nanosciences</strong><br />
C. H. Devillers, J.-C. Moutet, G. Royal, E. Saint-Aman. 9<br />
Chem. Commun., 2003, 888-889.<br />
R<br />
N<br />
R<br />
N<br />
G<br />
Zn<br />
R<br />
N<br />
N<br />
Fe<br />
N<br />
H<br />
Dynamic system
Cyclodextrins<br />
HO<br />
O<br />
O<br />
HO<br />
O<br />
HO<br />
OH<br />
HO<br />
O HO<br />
OH<br />
OH<br />
O<br />
HO<br />
O<br />
O<br />
OH<br />
O<br />
Lipophilic<br />
cavity<br />
HO<br />
HO<br />
OH<br />
O<br />
OH<br />
n<br />
Hydrophilic<br />
periphery<br />
Medical applications<br />
HO<br />
OH<br />
O<br />
OH<br />
O<br />
O<br />
OH<br />
=<br />
N<br />
H 3 C<br />
H<br />
N<br />
O<br />
O<br />
H 2 N<br />
O<br />
S<br />
OH<br />
H<br />
N<br />
O<br />
O<br />
N<br />
O<br />
N<br />
N<br />
NH<br />
O<br />
NH 2<br />
N<br />
N<br />
N<br />
H 2 N<br />
O<br />
HN<br />
O<br />
Solubilization of<br />
organic compounds<br />
R. Breslow, Acc. Chem. Res. 1995, 28, 146<br />
Y. Fukazawa et al., Tetrahedron. Lett., 2001, 42, 3203<br />
(drugs…) in water J. T. Rademacher, C. Czarnick, JACS, 1993, 3018<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
10
Self-Assembly<br />
onto surfaces<br />
R<br />
HS<br />
Ordered Self-Assembled Monolayer (SAM)<br />
Modification of surfaces<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
New materials<br />
11
"Clever<br />
Materials"<br />
“lotus effect”<br />
water<br />
water<br />
Hydrophylic<br />
surface<br />
hydrophobic<br />
surface<br />
Self-cleaning<br />
surfaces<br />
Zhong-Ze Ge, et al. Angew. Chem. Int. Ed. 2003, 42, 894-897.<br />
04/03/2008 W. Barthlott and C. Neinhuis, Planta, 1997, M1-<strong>Nanosciences</strong><br />
202, 1-8.<br />
12
Molecular Switches and Motors<br />
Stimulus<br />
Chemical<br />
Redox<br />
Photochemical<br />
State "0"<br />
(Stable)<br />
State "1"<br />
(Stable)<br />
Reversible modification of the<br />
physicochemical properties and geometry<br />
Molecular switch<br />
Molecular Motor<br />
Potential applications: molecular memories, responsive materials,<br />
electronic components, drug delivery …<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
13
A Biological Rotary Motor: ATP Synthase<br />
α<br />
β<br />
β<br />
γ<br />
α<br />
β<br />
α<br />
3<br />
Rotor<br />
H +<br />
γ<br />
2<br />
H +<br />
Bent axle also rotates,<br />
squashing each βunit in<br />
turn<br />
H +<br />
H +<br />
H + H +<br />
H + H +<br />
H + H + H +<br />
H + H<br />
H + + H +<br />
C<br />
H + H +<br />
H +<br />
C<br />
1<br />
C<br />
C<br />
H +<br />
Stator<br />
H + H +<br />
H +<br />
H + H + H +<br />
• Driving <strong>for</strong>ce : proton gradient<br />
• The rotation produces chemical energy in the <strong>for</strong>m of ATP<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
T. Elston, , H. Wang, G. Oster,<br />
Nature, 1998, 391, , 510.<br />
14
Photochemical Molecular switches<br />
hν<br />
K +<br />
K +<br />
Con<strong>for</strong>mational switches with azo derivatives<br />
Shinkai and Coll., J. Am. Chem. Soc.,<br />
1981, 103, , 111-115<br />
115<br />
04/03/2008 M1-<strong>Nanosciences</strong><br />
15
Chemical Molecular switches<br />
Rotaxanes<br />
stimulus<br />
"Molecular<br />
Shuttle"<br />
An acid/base<br />
controllable<br />
molecular shuttle<br />
See also F. Durola, J. P. Sauvage,<br />
Angew. Chem. In. Ed. , 2007, 46, 3537<br />
04/03/2008 (electrochemical molecular shuttle) M1-<strong>Nanosciences</strong><br />
V. Balzani, J. F. Stoddart and Coll., 16<br />
J. Am. Chem. Soc., 1998, 119, 12932-12941