Supramolecular Chemistry for Nanosciences

Supramolecular Chemistry
for Nanosciences
Guy Royal & L. P. Lévy
04/03/2008 M1-Nanosciences
1

Supramolecular chemistry
1987
Nobel prize to:
Donald J. Cram
Jean-Marie Lehn
Charles J. Pedersen
Jean-Marie Lehn
For their development
of the field of
supramolecular
chemistry
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Fundamentals of Supramolecular chemistry
● Host-Guest
chemistry
+
Selective
Host-Guest complex
(Supramolecule)
molecular
recognition
Host molecule
(Receptor)
Guest molecules
(Substrate)
● Hydrogen bonding
● π−π Stacking interactions
● Electrostactic interactions (ion-ion, ion-dipole, dipole-dipole)
● Van der Walls forces
● Hydrophobic/solvatophobic interactions
● Coordination bonds (Metal-donor bonds)
04/03/2008 M1-Nanosciences
Non-Covalent interactions
are involved
3

Fundaments of Supramolecular chemistry
● Host-Guest
chemistry
+
Selective
Host-Guest complex
(Supramolecule)
molecular
recognition
Host molecule
(Receptor)
Guest molecules
(Substrate)
O
O
O
O
O
O
K +
O
O
K +
O
O
O
O
[18]Crown-6
04/03/2008 M1-Nanosciences
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Fundaments of Supramolecular chemistry
● Host-Guest
chemistry
Host-Guest complex
(Supramolecule)
Host molecule
(Receptor)
+
Guest molecules
(Substrate)
Selective
Reversibility
molecular
recognition
● Reversibility:
- The thermodynamic equilibrium can be reached
- Dynamic architectures
- Change in constitution, shape, properties…
- Capacity of error correction (not available for fully covalent systems)
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Bottom-up Fabrication
design +
synthesis
Molecular
Components
self-assembly,
self-organization
FUNCTION
Shape, size, properties
(chemical, photochemical,
redox, …)
Supramolecular
System
Integration into device /
connexion to macroscopic world...
Nanomaterial
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design +
synthesis
What kind of molecules ?
Molecular
Components
Fe
N N
O
O
O
O
O
O
N
N
HS
R
"Building blocks":
- Complexing molecules
- Redox units
- Photosensitive molecules
- Conjugated or saturated molecules
- Carbon nanotubes, fullerenes…
- Molecules that can be attached onto a surface
- …
From very simple to very complex…
Only limited by imagination and… organic synthesis!!!
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design +
synthesis
What kind of molecules ?
Molecular
Components
Light absorbed
O
O
N
O
O
O
No Light emitted
N N
O
O
O
O
O
O
R
Self
assembly
K +
Photochemical
sensing and detection
Fe
N
N
HS
Light absorbed
O
O
N
K +
O
O
O
A. P. De Silva, S. A. De Silva,
J. Chem. Soc, Chem.
Commun., 1986, 1709
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Light emitted
8

Self-assembly
of molecular components
N
N
Zn
N
N
Fe
design +
synthesis
N
N
Zn
N
N
self-assembly
NHR
Fe
R
NH
R
Fe
N
R
N
N
HNR'
Zn
N
R
N
N
Zn
R'NH
N
N
R
Fe
Supramolecular structure
(dimer)
R
G
Guest species
(neutral molecule)
Application: electrochemical detection of guest molecules
04/03/2008 C. Bucher, M1-Nanosciences
C. H. Devillers, J.-C. Moutet, G. Royal, E. Saint-Aman. 9
Chem. Commun., 2003, 888-889.
R
N
R
N
G
Zn
R
N
N
Fe
N
H
Dynamic system

Cyclodextrins
HO
O
O
HO
O
HO
OH
HO
O HO
OH
OH
O
HO
O
O
OH
O
Lipophilic
cavity
HO
HO
OH
O
OH
n
Hydrophilic
periphery
Medical applications
HO
OH
O
OH
O
O
OH
=
N
H 3 C
H
N
O
O
H 2 N
O
S
OH
H
N
O
O
N
O
N
N
NH
O
NH 2
N
N
N
H 2 N
O
HN
O
Solubilization of
organic compounds
R. Breslow, Acc. Chem. Res. 1995, 28, 146
Y. Fukazawa et al., Tetrahedron. Lett., 2001, 42, 3203
(drugs…) in water J. T. Rademacher, C. Czarnick, JACS, 1993, 3018
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Self-Assembly
onto surfaces
R
HS
Ordered Self-Assembled Monolayer (SAM)
Modification of surfaces
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New materials
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"Clever
Materials"
“lotus effect”
water
water
Hydrophylic
surface
hydrophobic
surface
Self-cleaning
surfaces
Zhong-Ze Ge, et al. Angew. Chem. Int. Ed. 2003, 42, 894-897.
04/03/2008 W. Barthlott and C. Neinhuis, Planta, 1997, M1-Nanosciences
202, 1-8.
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Molecular Switches and Motors
Stimulus
Chemical
Redox
Photochemical
State "0"
(Stable)
State "1"
(Stable)
Reversible modification of the
physicochemical properties and geometry
Molecular switch
Molecular Motor
Potential applications: molecular memories, responsive materials,
electronic components, drug delivery …
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A Biological Rotary Motor: ATP Synthase
α
β
β
γ
α
β
α
3
Rotor
H +
γ
2
H +
Bent axle also rotates,
squashing each βunit in
turn
H +
H +
H + H +
H + H +
H + H + H +
H + H
H + + H +
C
H + H +
H +
C
1
C
C
H +
Stator
H + H +
H +
H + H + H +
• Driving force : proton gradient
• The rotation produces chemical energy in the form of ATP
04/03/2008 M1-Nanosciences
T. Elston, , H. Wang, G. Oster,
Nature, 1998, 391, , 510.
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Photochemical Molecular switches
hν
K +
K +
Conformational switches with azo derivatives
Shinkai and Coll., J. Am. Chem. Soc.,
1981, 103, , 111-115
115
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Chemical Molecular switches
Rotaxanes
stimulus
"Molecular
Shuttle"
An acid/base
controllable
molecular shuttle
See also F. Durola, J. P. Sauvage,
Angew. Chem. In. Ed. , 2007, 46, 3537
04/03/2008 (electrochemical molecular shuttle) M1-Nanosciences
V. Balzani, J. F. Stoddart and Coll., 16
J. Am. Chem. Soc., 1998, 119, 12932-12941