Michael W. Tausch

ValenciaOctobre, 2015

Experimental Approaches intoBasic Concepts of PhotochemistryLecture 1: Photoluminescence, Photoisomerisation

University Chemistry

of Wuppertal Education

Program

Curriculum Innovation

I: Why Photo-SciEd?

II: Basic Concept & Classification

III: Experiments & Applications

Outline:

Kristina Schottler

Makromolekulare Chemie

Wuppertal

Foto Atamari

Michael W. TauschChemistry & Chem. Educ.

Chemistry & Chem. Educ.

Michael W. Tausch

Dr. Claudia Bohrmann-

Linde

Prof. Dr. Simone Krees

Prof. Dr. Amitabh Banerji

Dr. Ralf-Peter Schmitz

Dr. Bernd Rohe

Rebecca Roggendorf

Heidrun Geller

René Krämer

Nico Meuter

Maria Heffen

Melanie Zepp

Heiko Hoffmann

Sebastian Spinnen

Ibeth Rendón Enríquez

Ingrid Reisewitz-Swertz

Renate Gärtig

David Nietz

Frederic Posalla

Saskia Ruckebier

u.v.a.

Valencia

2015

Spain

www.chemiedidaktik@uni-wuppertal.de

0 1

Photoprocesses in

Science Education

Photoprocesses in

Science Education

Life Science, e.g.:• in the photoreactor atmosphere

• in the photoreactor leaf

• in the photoreactor eye

• in the photoreactor skin

• in other natural systems

Material Science e.g.:• in photovoltaic cells

• in LED‘s and OLED‘s

• in research facilities

• in technical photoreactors

• in microelectronic devices

• in medicine

• in other man-made systems

Photoprocesses in

Science Education

Saving of Energy, e.g.:• in LED‘s und OLED‘s

• in solar reactors

• in climat control units with photochromic

and electrochromic windows

• in phototechnical procedures

Supply of Electrical Energy

from Sun Light, e.g.:• in photovoltaic cells

• in photoelectrochemical cells

• in fluorescence collectors (concentrators)

Sun Light Conversion and

Chemical Storage, e.g.:• in solar hydrogen, methane, methanol ..

• artificial photosynthesis products

2,5 ∙ 1022 J

3 ∙ 1024 J

100

Photoprocesses in

Science Education

Global Reserves (Mineral Oil, Natural Gas,

Coal, Uranium)

Annual Solar Radiation

Solar: 100 000 TW

Wind: 14 TW

Ocean Currents: 0.7 TW

Biomass: 5-7 TW

Hydroelectric: 1.2 TW

Geothermal: 1.9 TW

Source: Konarka, Arthur Norcik

Photoprocesses in

Science Education

Quelle: WBGU (Wiss. Beirat Globale Umweltveränderungen) des BMBF; September 2013

The Scinetific Advisory Board of the German Federal Ministery of Education and Research

Photoprocesses in

Science Education

The Jablonski Diagram

Paradigma (patron de pensiamiento):

„The „photo“ part of molecular photochemistry is a historical prefix and is now

too restrictive. It is now clear that electronically excited states of molecules

are the heart of all photoprocesses. The excited state is in fact an electronic

isomer of the ground state.“

N. J. Turro, Modern Molecular Photochemstry. Benjamin/Cummings, N.Y. (1978)

Photoprocesses in

Science Education

Light

S1→S0T1→S0

Luminescence: F, P, CL, EL, ECL

Energy transfer

Electron transferFurther reaction

types

Isomerization

Photovoltaics

Photoprocesses in

Science Education

Photoprocesses in

Science Education

• Coating of fluorescent lamps

• LED‘s for Lamps and displays

• OLED‘s for Lamps and displays

• Unforgeable documents & money

• Luminescent dyes for textiles etc.

• Fluorescence collectors

• Immunoassays (med. diagnose)

• Photodynamic therapy

• Fluorescence microscopy)

• Analytic methods (CL-Assay,

„Green Fluorescent Protein“

„Single Molecule Spectroscopy“)

Photoprocesses in

Science Education

Photoprocesses in

Science Education

Isamu Akasaki, Hiroshi Amano and Shuji Nakamura,

Nobel Price in Physics 2014 for the invention of blue LEDs

Stefan Hell, Eric Betzig and William Moerner,

Nobel Price in Chemistry for the invention of the STED-Nanoscopy

Photoprocesses in

Science Education

Paradigm: Atomic and molecular systems can exist in the electronic ground state

as well as (even for a short time) in electronically excited states.

M.Tausch, M. v. Wachtendonk , C. Bohrmann-Linde, S. Krees (Hrsg.), CHEMIE 2000+, C.C.Buchner, Bamberg (2007…2014)

The energy level model for molecules – A core concept in chemistry

excited state T1

τ = 10-2 – 102 s

excited state S1

τ = 10-9 – 10-8 s

Fluorescence

Phosphorescence

Exchange

of heat

lowest

unoccupied

energy level

highest

occupied

energy level

ground state So

M.T., D. Paterkiewicz, PdN-Chemie 36, 14 (1988); M.T., A. Grolmuss, M. Woock, PdN-Physik 47, 10 (1998); M.T., F.Gärtner, PdN-ChiS, 53, 20 (2004)

Photoprocesses in

Science Education

M. T. ,D. Paterkiewicz, PdN-Chemie 36, 14 (1988); M. T., A. Grolmuss, B. Piwek, PdN-Chemie, 47 (2), 10 (1998); … CHEMIE 2000+ (2007…2014)

www.chemiedidaktik.uni-wuppertal.de > Teaching Photochemistry

Photoprocesses in

Science Education

Photoprocesses in

Science Education

Melting 5 g

of tartric acidAdding 5 mg

of Aesculin

Mixing and distributing

the melted mass

Testing the photo-

luminescence

Fluorescence at

room temperaturePhosphorescence at

room temperature

Video

Videos: & Animations: www.chemiedidaktik.uni-wuppertal.de > Teaching photochemistry

Folie 25Nico Meuter

PhotolumineszenzChemie und ihre Didaktik

LUMO

Flu

ore

scence

E

HOMO

Absorp

tion

Photoprocesses in

Science Education

Videos: & Animations: www.chemiedidaktik.uni-wuppertal.de > Teaching photochemistry

Folie 26Nico Meuter

PhotolumineszenzChemie und ihre Didaktik

Absorp

tion

Phosphore

scence

LUMO

HOMO

E

Photoprocesses in

Science Education

Videos: & Animations: www.chemiedidaktik.uni-wuppertal.de > Teaching photochemistry

Folie 27Nico Meuter

PhotolumineszenzChemie und ihre DidaktikPhotoprocesses in

Science Education

Videos: & Animations: www.chemiedidaktik.uni-wuppertal.de > Teaching photochemistry

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1

380 430 480 530 580 630

Em

iss

ion

[a

. u

.]

Weavelength [nm]

Emission Spectra ofAesculine

in Tartrich Acid Matrix

red shift ≈100 nm

red shift ≈100 nm

Folie 28Nico Meuter

PhotolumineszenzChemie und ihre DidaktikPhotoprocesses in

Science Education

Videos: & Animations: www.chemiedidaktik.uni-wuppertal.de > Teaching photochemistry

excited state T1

τ = 10-2 – 102 s

excited state S1

τ = 10-9 – 10-8 s

Fluorescence

Phosphorescence

Exchange

of heat

Video: Fluo/Boric acid

Chl: Fluorescence

Car: no Fluorescence

Car Chl

Video Flash

www.chemiedidaktik.uni.wuppertal.de > Teaching photochemistry > Flash-Animationesn > Ein Fall für 2

Photoprocesses in

Science Education

A fantastic

couple

Green pumkin

seed oil

Fluorescence

No Fluorescence

M. W. Tausch. M. v. Wachtendonk , C. Bohrmann-Linde, S. Krees (Hrsg.) CHEMIE 2000+, C.C. Bucnhner (2001 …2014)

Flash

Photoprocesses in

Science Education

A fantastic

couple

In 1669 Hennig Brand discoverded the element phosphorus and the phenomenon of chemoluminescence

In igne succus omnium,

arte, corporum ...

Photoprocesses in

Science Education

with C. Bohrmann, ChiuZ 36 (3), 164 (2002) ; with J. Ibanez, C. Bohrmann -Linde u.a. J. Chem. Educ.. , 90 (4), 470 (2013)

(KOH + DMSO + Luminol)

www.chemiedidaktik.uni-wuppertal.de

Generation of the excited state

Chemical

reaction

Ground

state

Excided

state

Photoprocesses in

Science Education

American firefly

Photoprozesse in der Lehre

der Naturwissenschaften

Luminescent jellyfishes

Photoprocesses in

Science Education

The“ Glowing Razor Foil“

Self made-OLED‘s

• Basic-OLED

• Flexi-OLED

• Easy-OLED

• Quick-OLED

with A. Banerji, U. Scherf, M. T., Chemkon, 19 (1), 7 (2012); with A. Banerji, U. Scherf , M. T. , Educ. Quimica , 24 (1), 17 (2013)

with C. Bohrmann, ChiuZ 36 (3), 164 (2002) ; with J. Ibanez, C. Bohrmann -Linde u.a. J. Chem. Educ.. , 90 (4), 470 (2013)

www.chemiedidaktik.uni-wuppertal.de

Photoprocesses in

Science Education

Light

S1→S0T1→S0

Luminescence: F, P, CL, EL, ECL

Energy transfer

Electron transferFurther reaction

types

Isomerization

Photovoltaics

Photoprocesses in

Science Education

DIN A5 ca. 4 €

E.D.Bergmann, A.Weizmann, E.Fischer, JACS, 72, 5009 (1950), M. T., Chemkon, 3, 123 (1996)

S. Krees, PdN-ChiS, 62 (8), 35 (2013); M. T., PdN-ChiS, 64 (1) 5 (2015)

Polystyrol

Toluol

PET-Folie

Light

Darkness & Heat

Spiropyrane C19H18O3N2Merocyanine C19H18O3N2

10

1 Basic Experiment

2 Wavelength

3 Temperature

4 Solvent / Matrix

5 Thin Layer

Photoprocesses in

Science Education

Flash

Merocyanine Spiropyraneun foto-interruptor molecular

Photoprocesses in

Science Education

Polystyrene

Toluene

Spiropyran

Un Material

inteligente

Plastic Foil (PET)

Water, T = 60° C Ice&Water, T = 0° C

Erasing Storing

OverwritingWriting

S. Krees, PdN-ChiS, 61 ( 2) … (2012)

Photoprocesses

in Science Education

Angeregter

Zustand

Grundzustand

Thermische Reaktion vs. photochemische Reaktion

M. W.Tausch, Chemkon, 3, 123 (1996)

Thermischer

Reaktionsweg

Photochemischer

Reaktionsweg

M.Tausch, M.v.Wachtendonk (Hrsg.), CHEMIE 2000+, C.C.Buchner, Bamberg (2007…2010)

E.D.Bergmann, A.Weizmann, E.Fischer, JACS, 72, 5009 (1950)

Photochemical

Reaction

Pathway

Thermal

Reaction

Pathway

Reaction Coordinate

Photosteady

State

Photoprocesses in

Science Education

Flash

www.chemiedidaktik.uni-wuppertal.de

S. Spinnen, M. Essers, S. Krees, M. T., PdN-ChiS, 63, (2) 35 (2014); S. Spinnen, M. T. PdN-ChiS 64 … (2015); N. Meuter, M. T, PdN-ChiS, in press

Photoprocesses in

Science Education

Polar

Nano-Environment

(Nitrocellulose)

Mero Spiro

Non Polar

Nano-Enviroment

(Polystyrene)

SpiroMeroMero

Spiro

Beng Zhing Tang et al. „Aggregation-Induced Emission:

The Whole Is More Brilliant than the Parts“, Adv. Mat. DOI 10.1002 (2014)

S. Spinnen, M. Essers, S. Krees, M. T., PdN-ChiS, 63, (2) 35 (2014);

S. Spinnen, M. T. PdN-ChiS 64 … (2015)

Photoprocesses in

Science Education

S. Shinkai et al. Bull. Chem. Soc. Jap., 60, 1819, (1987)

V. Ramamurthy, Photochemistry in Organized and Constrained Media, VCH, (1991)

D. Wöhrle, M.W. Tausch, W.-D. Stohrer, Photochemie, Wiley-VCH, (1998)

… a Molecular

Trojan Horse

… a Molecular „Vise“

(„Screw Matrix“)

Photoprocesses in

Science Education

Ragnar S. Stoll, Stefan Hecht, Angew.Chem., 122 (30), 5176 (2010)

… a photoswitchable

(thermal) catalyst

accessible

basic/nucleophilic

center

Photoprocesses in

Science Education

M. Tausch, M.von Wachtendonk, C. Bohrmann-Linde, S. Krees (Hrsg.) Chemie 2000+ , C.C. Buchner, Bamberg (2002..2014)

K. Palczewski et al. „Crystal Structure of Rhodopsin...“. SCIENCE 289, 739 (2000)

M. T, M. Woock, A. Grolmuss: „Vom Lichtquant zum Sehreiz“, PdN (Physik), 47, 26 (1998)

… the photoswitch

in eye rhodopsine3 Millions of Retinal Cones

+ 100 Millions of Retinal Rods

Photoprocesses in

Science Education

Chemistry & Chem. Educ.

Michael W. Tausch

Dr. Claudia Bohrmann-

Linde

Prof. Dr. Simone Krees

Prof. Dr. Amitabh Banerji

Dr. Ralf-Peter Schmitz

Dr. Bernd Rohe

Rebecca Roggendorf

Heidrun Geller

René Krämer

Nico Meuter

Maria Heffen

Melanie Zepp

Heiko Hoffmann

Sebastian Spinnen

Ibeth Rendón Enríquez

Ingrid Reisewitz-Swertz

Renate Gärtig

David Nietz

Frederic Posalla

Saskia Ruckebier

u.v.a.