23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

Organizing supramolecular functional dye-zeolite crystalsUnidirectional antenna systems

UnidirectionalAntenna

Gion CalzaferriDepartment of Chemistry and BiochemistryUniversity of Bern, CH-3012 Bern, Switzerland

Unidirectional antenna materials for light harvesting, transport and trapping

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

3 Zeolite L is an ideal host for supramolecular organization of dyes

4 The stopcock principle: Functional stopcocks

6 New materials, an overview

2 An artificial antenna system: Concept

1 Light harvesting by green plants

5 Organizing supramolecular functional dye-zeolite crystals

Unidirectional antenna materials for light harvesting, transport and trapping

G. Calzaferri, A. Zabala Ruiz, H. Li 'Organizing supramolecular functional dye-zeolite crystals' Angew. Chem. Int. Ed., 2006, 45, 5408

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

X. Hu, K. Schulten, Phys. Tod. 50 (1997) 28

In natural photosynthesis, sunlight is absorbed by organized chlorophyll molecules.

This device allows fast energy transfer from electronically excited molecules to unexcited neighboring molecules in such a way that the probability for the excitation energy to reache the reaction center is very high.

1 Light harvesting by green plants

The aim of this work is to realize a similar light transport in an artificial system in which dye loaded zeolite L crystals adopt the antenna function.The role of the zeolite (host) is to prevent aggregation of the dyes, to superimpose a specific organization, and also to strongly improve the stability of the dyes.

The supramolecularly functionalized dye-zeolite crystals must be organized.

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

2 An artificial antenna system ConceptConceptmonodirectionalantenna materials

UnidirectionalAtenna

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

30 nm – 10’000 nm

96’000channels

600 nm

organized monomers30 nm crystal → 4800 dyes 38’000 dyes 60 nm

0.71 nm1.26 nm

3 Zeolite L is an ideal host for supramolecular organization of dyesOverviewOverview

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

K+oxonine

3 Zeolite L is an ideal host for supramolecular organization of dyesInsertion of dye molecules by Insertion of dye molecules by cationcation exchangeexchange

Nano-bulbs

DXP

Stefan Huber, Gion Calzaferri, ChemPhysChem, 2004, 5, 293.

3 Zeolite L is an ideal host for supramolecular organization of dyesInsertion of dye molecules by Insertion of dye molecules by byby gas phase loadinggas phase loading

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

O NN+

Orientation of Fluorescent Dyes in the Nano Channels of Zeolite L S. Megelski, A. Lieb, M. Pauchard, A. Drechsler, S. Glaus,C. Debus, B. A. J. Meixner, G. CalzaferriJ. Phys. Chem. B 105, 2001, 25-35

3 Zeolite L is an ideal host for supramolecular organization of dyesOrientation of fluorescent dyes in the channels of zeolite LOrientation of fluorescent dyes in the channels of zeolite L

Optical Spectroscopy of inorganic-organic host-guest nanocrystals organized as oriented monolayersS. Huber, A. Zabala Ruiz, H. Li, G. Patrinoiu, C. Botta, G. CalzaferriInorg. Chim. Acta, 2006, in press

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

3 Zeolite L is an ideal host for supramolecular organization of dyesExamples of dyes that have been insertedExamples of dyes that have been inserted

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

hν hν

Host-Guest Antenna MaterialsG. Calzaferri, S. Huber, H. Maas, C. Minkowski, Angew. Chemie, Int. Ed. 2003, 42, 3732

kEnT up to 3×1013 s-1

3 Zeolite L is an ideal host for supramolecular organization of dyesSequential insertion of dyes: PrincipleSequential insertion of dyes: Principle

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

M. Pauchard, S. Huber, R. Méallet, H. Maas, R. Pansu, G. Calzaferri, Angew. Chem. Int. Ed. 40 (2001) 2839

3 Zeolite L is an ideal host for supramolecular organization of dyesSequential insertion of dyes:Sequential insertion of dyes: Time and space resolved measurementsTime and space resolved measurements

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

C. Minkowski, G. Calzaferri, Angew. Chem.Int. Ed. 2005, 44, 5325

*

0

1

1 D A

PRR

α=⎛ ⎞

+ ⎜ ⎟⎝ ⎠

0.27 ns0.45 ns0.89 ns

0.13 ns 9

1116

23

3 Zeolite L is an ideal host for supramolecular organization of dyes1D 1D FFöörster Energy Transferrster Energy Transfer

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

G. Calzaferri, US + EU patent, (priority date 2000, granted US 2005, EU 2006)

4 The stopcock principleFunctional stopcocksFunctional stopcocks

I) Reversible stopcocks

III) Covalently bound stopcocks. (Bonding via –Si-O-Si- and –Si-O-Al- .)

II) Electrostatically bound stopcocks

Sequential Functionalization of the Channel Entrances of Zeolite L CrystalsS. Huber, G. Calzaferri, Angew. Chem. Int. Ed. 2004, 43, 6738-6742.

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

Trapping Energy from and Injecting Energy into Dye-Zeolite NanoantennaeH. Maas, G. Calzaferri, Angew. Chemie, Int. Ed. 2002, 41, 2284

4 The stopcock principleFirst successful experimentsFirst successful experiments

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

Trapping Energy from and Injecting Energy into Dye-Zeolite NanoantennaeH. Maas, G. Calzaferri, Angew. Chemie, Int. Ed. 2002, 41, 2284

4 The stopcock principleFirst successful experimentsFirst successful experiments

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

Bossart, De Cola, Welter, CalzaferriChem. Eur. J., 2004, 10, 5771

1.84 nm

4 The stopcock principleInjecting electronic excitation energy into an artificial antennInjecting electronic excitation energy into an artificial antenna by a a by a RuRu 2+2+ complexcomplex

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

G. Calzaferri, A. Zabala Ruiz, H. Li, S. Huber, Paten pend. priority date Juli 2005Arantzazu Zabala Ruiz, Huanrong Li, Gion Calzaferri, Angew. Chem.Int Ed. 2006, 45, 5408

5 Organizing supramolecular functional dye-zeolite crystalsCreating a unidirectional antenna systemCreating a unidirectional antenna system

unidirectional materials

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

5 Organizing supramolecular functional dye-zeolite crystalsOrganized unidirectional antenna crystalsOrganized unidirectional antenna crystals

Arantzazu Zabala Ruiz, Huanrong Li, Gion CalzaferriAngew. Chem.Int Ed. 2006, 45, 5408

monodirectionalantenna materials

UnidirectionalAtenna

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

Light-harvesting host-guest antenna materials for photonic devicesCalzaferri, Huber, Devaux, Zabala Ruiz, Li, Bossart, DieuProc. of SPIE, Organic Optoelectronics and Photonics II, Vol. 6192 2006 619216-1 -9.

5 Organizing supramolecular functional dye-zeolite crystalsUnidirectional antenna, evidence by fluorescence microscopyUnidirectional antenna, evidence by fluorescence microscopy

Optical Spectroscopy of inorganic-organic host-guest nanocrystals organized as oriented monolayersS. Huber, A. Zabala Ruiz, H. Li, G. Patrinoiu, C. Botta, G. Calzaferri, Inorg. Chim. Acta, 2006, in press

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

5 Organizing supramolecular functional dye-zeolite crystalsUnidirectional antenna, spectroscopic evidenceUnidirectional antenna, spectroscopic evidence

Optical Spectroscopy of inorganic-organic host-guest nanocrystals organized as oriented monolayersS. Huber, A. Zabala Ruiz, H. Li, G. Patrinoiu, C. Botta, G. Calzaferri, Inorg. Chim. Acta, 2006, in press

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

R.Q. Albuquerque, A. Zabala Ruiz, H. Li, L. De Cola, G. Calzaferri, Proc.of SPIE, Vol. 6197 2006 61970B-1 5.

Mean length: 250 nmAspect ratio: 0.3

0.41 (156 ns) + 0.59 (1090 ns) 0.37 (178 ns) + 0.63 (1016 ns)

0.0

0.5

1.0

450 500 550 600 650 700 750 800 850

Wavelength (nm)

Inte

nsity

(a.u

)

Monolayer / O2Delay = 200 ns

450 500 550 600 650 700 750 800 850

Wavelength (nm)In

tens

ity(a

.u)

0.0

0.5

1.0Monolayer / N2Delay = 200 ns

5 Organizing supramolecular functional dye-zeolite crystalsEvidence by lEvidence by luminescenceuminescence quenching by Oquenching by O22 of a Ruof a Ru2+2+ complex attached to zeolite Lcomplex attached to zeolite L

R. Q. Albuquerque, Z. Popovic, L. De Cola, G. Calzaferri, ChemPhysChem, 2006, 07, 1050-1053.

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

stopcock pluggedantenna material

antenna materialmixed dye materialsingle dye material

6 New dye-zeolite guest-host materialsAn overviewAn overview

Refractive index matching

patent pend. with Optical Additives + Clariant

monodirectionalantenna materials

UnidirectionalAtenna

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

Organization and solubilizatio of zeolite crystalsO. Bossart, G. Calzaferri, Chimia 60, 2006, 179O. Bossart, PhD thesis, DCB Univ. of Bern, in preparation.L. De Cola, Z Popovic, S. Huber, G. Calzaferri, in prep.

2 mμ

Hexagonal Network Organization of Dye-loaded Zeolite L Crystals by Surface Tension Driven Auto-assemblyS. Yunus, F. Spano, A. Bolognesi, C. Botta, G. Patrinoiu, D. Brühwiler, A. Zabala Ruiz, G. Calzaferri, Adv. Func. Mater. 2006, in press

6 New dye-zeolite guest-host materialsOrganizingOrganizing thethe crystalscrystals

Organizing supramolecular functional dye-zeolite crystalsA. Zabala Ruize, H. Li, G. Calzaferri, Angew. Chem. Int. Ed.2006, 45, 5408

23rd European Crystallographic Meeting, Leuven 6-11 August 2006, Lecture given by Gion Calzaferri

Dr. Rodrigo Queiroz de Albuquerque, Dr. Takayuki Ban, Dr. Dominik Brühwiler, Olivia Bossart, Dr. Antonio Currao, Dr. André Devaux, Dr. Niklaus Gfeller, Dr. Stephan Glaus, Dr. Stefan Huber, Katsiaryna Lutkouskaya, Dr. Abderrahim Khatyr, Dr. Claudia Leiggener,Dr. Huanrong Li, Dr. Huub Maas, Dr. Marc Meyer, Dr. Silke Megelski, Dr. Claudia Minkowski, Dr. Marc Pauchard, Dr. Michel Pfenniger, Dr. Stephane Suarez, Dr. Marieke van Veen, Dr. Mikalai Yastkou, Dr. Arantzazu Zabala Ruiz, René Bühler

EU: Nanochannel (European Union RTN) new Nanomatch

NRP 47: Energy collection, transport and trapping by supramolecular organization of dyes in hexagonal zeolite nanocrystals

NF: Luminescent molecules and quantum dots in the cavities of zeolites

CLARIANT: Dye-loaded zeolite L materials

Collaboration: Austria, Belarus, Belgium, France, Germany, Italy, Netherlands, Switzerland etc.

BFE: Transformation and storage of solar energy

Roche Roche Diagnostics (MBF project INDia)

KTI Kommission for technical innovation