Leclere Oral Session 5

7/31/2019 Leclere Oral Session 5

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White Light EmittingWhite Light EmittingSupramolecularSupramolecular PolymersPolymers

PhilippePhilippe LECLERELECLERE


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Recent challenge: towards lighting Recent challenge: towards lighting

IntroductionIntroduction

Philips

Siemens

UDC


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


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How toHow to produceproduce white light ?white light ?

MixingMixing of of threethree REDRED,, GREENGREEN, and, and BLUEBLUEemittingemitting chromophoreschromophores

Blends

Multilayers

Block Copolymers Quantum dots


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SupramolecularSupramolecular PolymersPolymers

o o a ggrega evan der Waals interactions Covalent bonds

Supramolecular PolymerNon-covalent interactions


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SupramolecularSupramolecular Polymers Polymers

TwoTwo approachesapproaches ......

SupramolecularSupramolecular polymerpolymer chainchain

SupramolecularSupramolecular oligomeroligomer stackstack


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Quadruple HydrogenQuadruple Hydrogen- -Bonded UnitBonded Unit

NN

O

N HH

RN

N

NH HC

NHO

R

R'


C N HO

R'O

Intramolecular H-bond

Intermolecular H-bonds

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

UreidopyrimidinoneUreidopyrimidinone ( (UPyUPy))


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FirstFirst ApproachApproach

NN

O

N HHC

N HO

R

R'

NN

O

NH HC

NHO

R

R'

RR RRUPyUPy

HH -- bondingbonding

MixingMixing

UV Excitation

n m p q


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SupramolecularSupramolecular Polymers Polymers

PerylenePerylene - - PERYPERY

M.M. PouderoijenPouderoijen

para para --PhenylenePhenylene vinylenevinylene OPV5OPV5

FluoreneFluorene F3F3

Ch. GrenierCh. Grenier

R.R. AbbelAbbel


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Purification by recycling GPCPurification by recycling GPC


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In SolutionIn Solution

0.50

0.75

1.00

r m .

P L i n t .

0.50

0.75

1.00

r m .

A b s .

0.50

0.75

1.00

r m .

P L i n t .

0.50

0.75

1.00

r m .

A b s .

Absorption Photoluminescence

400 500 600 700 800

0.00

0.25 n o

(nm)

300 400 500 600 700 800

0.00

0.25

n

(nm)

400 500 600 700 800

0.00

0.25 n o

(nm)

300 400 500 600 700 800

0.00

0.25

n

(nm)

n

n

nPERYF3

OPV5


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InIn SolidSolid StateState

0.50

0.75

1.00

r m .

P L i n t .

0.50

0.75

1.00

r m .

A b s .

0.50

0.75

1.00

r m .

P L i n t .

0.50

0.75

1.00

r m .

A b s .


400 500 600 700 800

0.00

0.25 n o

(nm)

300 400 500 600 700 800

0.00

0.25

n

(nm)

400 500 600 700 800

0.00

0.25 n o

(nm)

300 400 500 600 700 800

0.00

0.25

n

(nm)

n

n

n

OPV5

F3 PERY


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nn

= 0.783 nm= 0.783 nm = 0.452 nm= 0.452 nm

SmoothSmooth surfacessurfaces


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0.25

0.50

0.75

1.00

E L i n t . n o

r m .

ITOPEDOT:PSS

emissive layerAl

nOPV5

nF3

nPERY

400 500 600 700

0.00

0.25

0.50

0.75

1.00

1.25

P L i n t . ( a r b . u

n i t s

)

((((nm )

400 500 600 700

.

(nm)

Glass

W.W. StouwdamStouwdam

85 : 10 : 5

exc = 365 nm


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InIn SolidSolid StateState 8585 :: 1010 :: 55

= 0.754 nm= 0.754 nm

No phaseNo phase separationseparation


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SupramolecularSupramolecular OligomerOligomer StackStack

SecondSecond ApproachApproach

FFF =FFF = FluoreneFluoreneFNF =FNF = NaphtaleneNaphtaleneFQF =FQF = QuinoxalineQuinoxalineFBF =FBF = BenzothiadiazoleBenzothiadiazole

FTF =FTF = ThienopyrazineThienopyrazine

FFF FNF FQF FBF FTF

R. Abbel


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5

1.5x10 5

C12-F1-C12C12-F3-C12C12-FNF-C12

a b

5

1.5x10 5

C12-F1-C12C12-F3-C12C12-FNF-C12

a b



F1F1F3FNF

300 400 500 600 7000.0

5.0x104

.C12-FQF-C12C12-FBF-C12C12-FTF-C12

( M - 1 c m -

1 )

(nm)

400 500 600 700 800

P L i n t

.

(nm)300 400 500 600 700

0.0

5.0x104

.C12-FQF-C12C12-FBF-C12C12-FTF-C12

( M - 1 c m -

1 )

(nm)

400 500 600 700 800

P L i n t

.

(nm)

R. Abbel

FQFFBFFTF

Small changes Small changes bigbig effectseffects on the photoluminescenceon the photoluminescence propertiesproperties


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MolecularMolecular ModellingModelling

FFF

FTF

DreidingDreiding Force FieldForce Field M. Surin

FNF

FBF

FQF

FNF FFF, FQF, FBF, FTFFNF FFF, FQF, FBF, FTF


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FFFFFF

2.0 m 300 nm

HeightHeight = 4.3 nm= 4.3 nm


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Annealed @ 125C


ExtrudedExtruded filamentfilamentFFFFFF

30C

W. PisulaLamellarLamellar organizationorganization perpendicularperpendicular to the filament axisto the filament axis


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MolecularMolecular ModellingModelling


M. SurinPeriodicPeriodic BoundaryBoundary ConditionsConditions


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Hierarchical OrganizationHierarchical Organization

FFFFFF


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OrganogelsOrganogels

Spin coatingDrop Casting

FTFFTF

2.0 m400 nm

MCHMCH


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OrganogelsOrganogels

FFFFFF FTFFTF

MCHMCH

Gel

Sol


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White EmittingWhite Emitting OrganogelsOrganogels

exc = 375 nm= 375 nm

FFF : FQF : FBF : FTF4.47 : 0.65 : 0.23 : 0.1 mM

POMPOM AFMAFM


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SupramolecularSupramolecular approachapproach c combinesombines the purity of the purity of oligomersoligomers with thewith the processabilityprocessability of polymers :of polymers :

Self Self--complementarycomplementary UPyUPy group equippinggroup equipping chromophoreschromophores; ; --stacking and Hstacking and H- -bonding.bonding.

ThisThis modularmodular a roacha roach isis aa romisinromisin a roacha roach toto

SummarySummary

createcreate multicomponentmulticomponent systemssystems. . EasyEasy toto processprocess and noand no macrophasemacrophase separation isseparation is

observed.observed.

ColorColor tuningtuning by simpleby simple mixingmixing of chromophores.of chromophores. MechanismsMechanisms of (whiteof (white- -lightlight emittingemitting) ) organogelorganogel

formation.formation.


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AcknowledgementsAcknowledgements

Service de Chimie des Matriaux Nouveaux

Universit de MonsMons (Belgium)

M. Surin

R. Lazzaroni

Eindhoven University of Technology

Eindhoven (The Netherlands)

R. Abbel

Ch. GrenierW. StouwdamM. PouderoijenA.P.H.J. Schenning

E.W. Meijer

Max Planck Institute fr PolymerforschungMainz (Germany)

W. Pisula


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AcknowledgementsAcknowledgements

European Commission.

Belgian Federal Government Office of Science Policy.

Fonds National pour la Recherche Scientifique (FNRS, Belgium).

overnmen o e g on a onne.

Communaut franaise de Belgique.


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Thank you for attention !!Thank you for attention !!

Documents

Leclere Oral Session 5