White Light Emitting Supramolecular Polymers

Philippe LECLERE

Introduction
Recent challenge: towards lighting

Philips UDC

Siemens

Introduction

http://www.oled-display.net/oled-lighting

Introduction
How to produce white light ?
Mixing of three RED, GREEN , and BLUE emitting chromophores RED,

Blends Multilayers Block Copolymers Quantum dots

Introduction
Supramolecular Polymers

Colloidal Aggregate van der Waals interactions

Macromolecule Covalent bonds

Supramolecular Polymer Non-covalent interactions

Supramolecular Polymers

Two approaches ... Supramolecular polymer chain

Supramolecular oligomer stack

Supramolecular Polymers
Quadruple Hydrogen-Bonded Unit HydrogenR' O R N H O C N H O R' H N C O H N H N N N R N H

Intramolecular H-bond

Intermolecular H-bonds

Ureidopyrimidinone (UPy) UPy)

Science, 278, 1601 (1997) J. Polym. Sci., Part A: Polym. Chem. 37, 3657 (1999) Chem. Comm. 1847 (1998)

Supramolecular Polymers
First Approach
R' H N C O H N H R N N N N R H N H O C O N H O R'

UPy
H - bonding

Mixing

UV Excitation

Supramolecular Polymers

Perylene - PERY M. Pouderoijen

parapara-Phenylene vinylene OPV5 Ch. Grenier

Fluorene F3 R. Abbel

Purification by recycling GPC

Supramolecular Polymers
In Solution
a
1.00 0.75 norm. PL int. norm. Abs.

Absorption

b
1.00 0.75

Photoluminescence

0.50

0.50

0.25

0.25

0.00 300 400 500

(nm)

0.00 600 700 800 400 500 600

(nm)

700

800

F3

PERY

n
OPV5

n n

Supramolecular Polymers
In Solid State
Absorption
1.00

d
1.00

Photoluminescence

0.75 norm. PL int. 400 500

(nm)

0.75

norm. Abs.

0.50

0.50

0.25

0.25

0.00 300 600 700 800

0.00 400 500 600

(nm)

700

800

F3

PERY

n
OPV5

n n

Supramolecular Polymers
In Solid State
n n

= 0.452 nm

= 0.783 nm

Smooth surfaces

Supramolecular Polymers
In Solid State
EL int. norm.
1.00 0.75

PERY OPV5 F3

n n n

0.50 0.25 0.00 400 500 600 700

Al emissive layer PEDOT:PSS ITO Glass

(nm)
1.25

PL int. (arb. units)

1.00 0.75 0.50 0.25 0.00 400 500

85 : 10 : 5

600

700

exc = 365 nm

(nm)

W. Stouwdam

Supramolecular Polymers
In Solid State 85 : 10 : 5 No phase separation
= 0.754 nm

Supramolecular Oligomer Stack

Second Approach

FFF FFF = Fluorene FNF = Naphtalene FQF = Quinoxaline FBF = Benzothiadiazole FTF = Thienopyrazine

FNF

FQF

FBF

FTF

R. Abbel

Supramolecular Oligomer Stack

Absorption
1.5x10
5

b
C12-F1-C12 F1 F1 C12-F3-C12 F3 C12-FNF-C12 FNF C12-FQF-C12 FQF C12-FBF-C12 FBF C12-FTF-C12 FTF

Photoluminescence

1.0x10
(M cm )
-1 -1

5.0x10

0.0 300 400 500

(nm)

PL int. 400

600

700

500

600
(nm)

700

800

Small changes big effects on the photoluminescence properties

R. Abbel

Molecular Modelling
FTF FFF

FQF FNF FNF <> FFF, FQF, FBF, FTF

M. Surin

FBF Dreiding Force Field

Supramolecular Oligomer Stack

FFF

2.0 m

300 nm

Height = 4.3 nm

Supramolecular Polymers

FFF
30C

Extruded filament
Annealed @ 125C

Lamellar organization perpendicular to the filament axis

W. Pisula

Supramolecular Oligomer Stack

Molecular Modelling

Periodic Boundary Conditions

M. Surin

Hierarchical Organization

FFF

Organogels

FTF
Drop Casting Spin coating

400 nm

2.0 m

MCH

Organogels

FFF

FTF

Gel Sol

MCH

White Emitting Organogels

FFF : FQF : FBF : FTF 4.47 : 0.65 : 0.23 : 0.1 mM

exc = 375 nm

POM

AFM

Summary
Supramolecular approach combines the purity of oligomers with the processability of polymers :
Self-complementary UPy group equipping chromophores; Selfchromophores; -stacking and H-bonding. H-

This modular approach is a promising approach to create multicomponent systems. systems. Easy to process and no macrophase separation is observed. Color tuning by simple mixing of chromophores. Mechanisms of (white-light emitting) organogel (whiteemitting) formation.

Acknowledgements

Service de Chimie des Matriaux Nouveaux Universit de Mons Mons (Belgium)

M. Surin R. Lazzaroni

Max Planck Institute fr Polymerforschung Mainz (Germany) Eindhoven University of Technology Eindhoven (The Netherlands)

W. Pisula

R. Abbel Ch. Grenier W. Stouwdam M. Pouderoijen A.P.H.J. Schenning E.W. Meijer

Acknowledgements

European Commission. Belgian Federal Government Office of Science Policy. Fonds National pour la Recherche Scientifique (FNRS, Belgium). Government of the Rgion Wallonne. Communaut franaise de Belgique.

Thank you for attention !!