M1 Nanosciences

Guy Royal

Description

Niveau: Supérieur, Master, Bac+4
104/03/2008 M1-Nanosciences Some of our own work… N N N N H HH H Cyclam - Formation of strong complexes with transition metal cations M - Can be chemically modified in various ways by functional groups Functional groups (coordinating, photosensitive, redox…) A real molecular platform

• fe fe


• tetrasubstituted cyclam-copper


• cyclam


• transition metal


• metal complexes


• visible spectroscopyfefe


• functional group


• reproducible processes

Sujets

• Cyclam
• Transition metal
• Coordination complex
• Functional group

Informations

• Publié par: larec
• Publié le: 01 mars 2008
• Nombre de lectures: 6
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

A real molecular platform

M

- Formation of strong complexes with transition metal cations

Cyclam

Functional groups (coordinating, photosensitive, redox…)

- Can be chemically modified in various ways by functional groups

of our

Some

own

work

M1-Nanosciences

04/03/2008

M

04/03/2008

Stereochemistry of metal complexes of cyclam

Type III

Type I

Type IV

Type II

Type V

Electrochemical input ? Reversible change in the geometry

M1-Nanosciences

2

Fe

Fe

Me

Me

Characterization of tetrasubstituted cyclam-copper complexes

N N CuII N N

L CuII Type I

N N CuI N N

L CuI Type V

Me

Fe

Fe

Me

00 2 8 air-stable complexes

M1-Nanosciences

e-

3

?

Fe

Me

N N CuII N

e-

Me

Fe

Potentiostatic electrolyses followed by UV-visible Spectroscopy

Absorbance (λ= 600 nm) vs time Oxidation Potential : + 0 V ; Reduction Potential : - 0,8 V

II ε LCu 1000

800

600

400

200

0

Reversible and reproducible processes

400

Buch 0 e 4/ r 0 , 3/ M 20 o 0 u 8 tet, Pécaut, Saint-Aman, Roya M l; 1   - I N n a o n r o g s . c   ie C nc h e e s m.,2004,43, 3777

500

-0.6

600

-0.4 E /V

ε LCu I LCu II LCu I 250 200

700

I

-0.2

λ(nm)

800

150

100

50

0

N

04/03/2008

N

N

M N N

N

Second example:  switchable supramolecular materials

N

N

N

Terpyridine subunit

N

NH

HN

N

N

N

N

2 kinds of coordination groups

M1-Nanosciences

5

N N N

,

N HN

NH N

=

Second example: switchable supramolecular materials

1 eq.

1 eq.

N N

N

= Cu2+, Co2+, Fe2+, Ni2+or Zn2+

04/03/2008

1 eq.

1 eq.

Heterometallic coordination polymer

Gel

A real molecular material

M1-Nanosciences 6 A. Gasnier, C. Bucher, J.-C. Moutet, E. Saint-Aman, P. Terech, G. Royal,in preparation

N N N

=

N HN

NH N

Redox active molecular

N N

N

Long Polymer chains

+ 1V  

materials

Redox-active materials

- 0.4V

Oligomers

Co2+ Co3+ GelLiquid Stimuli responsive molecular material

04/03/2008 A. Gasnier, C. Bucher, J.-C. Moute M t, 1   - E N . a   n S o a s i c n i t e - n A ce m s an, P. Terech, G. Royal,in preparation

7

N

N

N

N

M N

04/03/2008

N

Third example: pH-Triggered Molecular

N

N

N

N HN

NH

N

O

N

Terpyridine O subunit 2 amide groups: Poor complexing macrocycle

N

N

N

Acid

N

N

O

Base

N

N

O

N

switch

N

N

N

N

Powerf M ul 1-Nanosc l i e e x n i ce n s g macrocycle comp

=

=

8

N N N

O NHN

NH N O

= Cu2+

N N N

Acid +

pH-Triggered

"Monomer form"

Molecular

switch

Translocation process

"Polymer form"

+ Base

04/03/2008 M1-Nanosciences 9 A. Gasnier, J.-M. Barbe, C. Bucher, F. Denat, J.-C. Moutet, E. Saint-Aman, G. Royal,submitted

Cyclam: a molecular platform 

Electrochemical motor

04/03/2008

e-

M

Electrochemical switch

M1-Nanosciences

ch

l switch

+ 1V

- 0.4V

design + synthesis

Molecular Components

- Drop casting - Encapsulation into polymer matrix - Covalent grafting - Self-assembled monolayers - Langmuir-Blodgett films - …

04/03/2008

Bottom-up Fabrication

self-assembly, self-organization

Supramolecular System

Integration into solid devices / connexion to the macroscopic world...

M1-Nanosciences

Nanomaterial

11