SUPRAMOLECULAR PHOTONICSSUPRAMOLECULAR PHOTONICS

Absorbance of light (190-750 nm) Absorbance of light (190-750 nm) by substanceby substance

Energy levels of molecular orbitals in formaldehyde (HOMO: Energy levels of molecular orbitals in formaldehyde (HOMO: Highest Occupied Molecular Orbitals; Highest Occupied Molecular Orbitals;

LUMO: Lowest Unoccupied Molecular Orbitals) LUMO: Lowest Unoccupied Molecular Orbitals) and possible electronic transitionsand possible electronic transitions

Possible de-excitation pathways Possible de-excitation pathways of excited moleculesof excited molecules

Fluorescent probesFluorescent probes

The success of fluorescence as an investigative tool in studying the structure and dynamics of matter or living systems arises from the high sensitivity of fluorometric techniques, the specificity of fluorescence characteristics due to the micro environment of the emitting molecule, and the ability of the latter to provide spatial and temporal information.

Various parameters influencing the emission Various parameters influencing the emission of fluorescenceof fluorescence

Information provided by fluorescent probes Information provided by fluorescent probes in various fieldsin various fields

Fluorescent reagentFluorescent reagent

M+n

((Change the position of fluorescent bandChange the position of fluorescent band))

D. Knapton, M. Burnworth, S. J. Rowan, C. Weder, Angew. Chem. Int. Ed. 2006, 45, 5825–5829

Fluorescent reagentsFluorescent reagents

Binding mode

Fluorescent reagents for DNAFluorescent reagents for DNA

Fluorescent reagents for DNAFluorescent reagents for DNA

500 600 7000

250

500

750

1000 A

Flu

ore

sce

nce

inte

nsi

ty /

a.u

.

Wavelength / nm

λabs

/ nm λ

fl / nm

free bound

K

(104

M−1

)

n

free bound

I

max /

Io

1 395 403 18 3.5 544 518 28 2 395 400 21.8 4.4 549 526 74

N+

N+

O

O

O

O

O

O

O

O

O

O

N+

N+

O

O

O

O

O

O

O

O

O

O

1

2

Optical methods for intercalation Optical methods for intercalation analysisanalysis

Fluorescence microscopy in intercalation Fluorescence microscopy in intercalation analysisanalysis

Fluorescent reagents for DNAFluorescent reagents for DNA

DNA cleavage reagentDNA cleavage reagent

DNA cleavage reagentDNA cleavage reagent

PPCCTT cationcation sensorssensors((PPhotoinducedhotoinduced Charge T Charge Transfer)ransfer)

P. Jiang, Z. Guo, Coordination Chemistry Reviews, 248 (2004) 205–229

PPCCTT cationcation sensorssensors

Free

Bound

exite

360nm

360nm

emmit

540nm

460nm

ns

3

22

P. Jiang, Z. Guo, Coordination Chemistry Reviews, 248 (2004) 205–229

h

Non-fluorescent complexя

Zn2+

h

Intensive fluorescence at 770 nm,increase of life time of exited statefrom 1.4 ns up to 84 ns

(LMCT)e-

M. H. Keefe, K. D. Benkstein, J. T. Hupp, Coordination Chem. Reviews, 205 (2000) 201–228

LMCT LMCT cationcation sensorssensors((Ligand-Metal Charge TLigand-Metal Charge Transfer)ransfer)

T / °C Log K1 Log K2

10 3.637+-0.01 4.8+-0.1520 3.578+-0.01 4.7+-0.1530 3.546+-0.01 4.7+-0.1540 3.467+-0.01 4.8+-0.15

N S

OO

O

O

O

N S

OO

O

O

O

low fluorescent responselow solubility in water

1

Cyclodextrin-based sensor systemCyclodextrin-based sensor system

2 3

S

N

O

O

O

OO

Molecule 1

Molecule 2

h (Molecule 1)*

Molecule 2

(Molecule 1)*

Molecule 2

Excimer-basedExcimer-based cationcation sensorssensors

red-shift of the emission spectrum

Excimer-basedExcimer-based cationcation ssensorsensors: : non-cyclic ethers with two naphthalenes

Calixarene-based Calixarene-based fluorescent fluorescent molecular sensors molecular sensors for lead ionsfor lead ions

e-

Molecule Dipoleh

+ -

life time of dipole 10-10 sek

Supramolecule Dipoleh

+ -

e-

e-

e-

PET systemsPET systems(Photoinduced Electron Transfer)(Photoinduced Electron Transfer)

life time of dipole 10-1 sek

PET systemPET system- e

-

Ru2+ Ru3+ Re(I), Os(II)

Ru-AB-Re 0.93; 1,17 Redox potentials (V)

109 сек-1

S. Campagna , C. Di Pietro, F. Loiseau, B. Maubert, N. McClenaghan, R. Passalacqua, F. Puntoriero, V. Ricevuto, S. Serroni, Coordination Chem. Reviews, 229 (2002) 67/74

emission 802 нм

h

h

PET systemPET system

S

h

S

- e-

,+

.PET systemPET system

PET systemPET system

PhotovoltaicPhotovoltaic PerformancePerformance

M. Narutaki, K. Takimiya, T. Otsubo, Y. Harima, H. Zhang,Y.Araki, O. Ito, J. Org. Chem. 2006, 71, 1761.

Al/ organic film /Au covered electrode

Photocurrent generatedwere measured and converted into the incident photon-to-current conversion efficiencies (IPCE).

Side view of multilayer organic EL devices andmolecular structures of the materials used

MaterialsMaterials for OLED for OLED

A, B, C, and D corresponding to n = 0, 1, 2 and 3 inFlAMB-1n

K4Fe(СN)6

Photocontrolled electron Photocontrolled electron transporttransport

Lipid bilayer membraneLipid bilayer membraneAnthraquinone disulfonic acid

disodium salt

Fluorescence resonance energy Fluorescence resonance energy transfer transfer

Materials for fluorescence Materials for fluorescence resonance energy transfer resonance energy transfer

Tb+3

Fluorescence resonance energy Fluorescence resonance energy transfer transfer

h300nm)

Energy transfer

Increase of fluorescence intensity in 680 times!!!!

AA plugplug –– socketsocket systemsystem

Switching of photoinduced energy transfer by acid/based controlled plug in/plug out of suitable molecular components

Dethreading/rethreadingDethreading/rethreading ofof pseudorotaxanespseudorotaxanes

N+

N+

RR N+

N+

RR

N+

R N+

R N+

R N+

R

e-

AA supramolecularsupramolecular systemsystem thatthat behavesbehaves

asas aa molecular-levelmolecular-level extensionextension cablecable

PhotochemicallyPhotochemicallyddrivenrivenmmolecularolecularmachinemachine

R. BALLARDINI,V. BALZANI, A. CREDI, M. T. GANDOLFI, M. VENTURI, Acc. Chem. Res. 2001, 34, 445-455

PhotochemicallyPhotochemically d drivenriven m molecularolecular machinemachine

200 250 300 350 400 450

0,0

0,5

1,0

1,5 А

B в А

А в B

Absorbance

Wavelength / nm

h1

h2

A B

R1

R2H

H R1 R2

H H

h1

KT,h2

trans-cis-isomerizationя

R4

R3R1

R2

R1

R2 R4

R3

O OH

h1

h2

+ cycloaddition

electrocyclic reaction

h1

KT, h2

h1

h2

spironaphthoxazine, chromene fulgide, dihetarylethene

PhotochPhotochromic romic systemssystems

OO

N

OO

O

N

O

O

O

O

O

Ca2+

h

logK1 = 4.8 logK1 = 1.9

PhotocPhotocontrolled complex ontrolled complex formationformation

NN

NH

LysPapain

O N

NNH

LysPapain

O

NH

NO2

O

NH

(CH2)3NH

H3N

NH

O

O

NH

(CH2)3NH

H3N

NH

O

OH NO2NH2

h1(400nm)

h2(320nm)

+

+

+

does not participate inhydrolysis process

PhotocPhotocontrolled hydrolysis ontrolled hydrolysis processprocess

PhotochPhotochromic systems in romic systems in industryindustry

ConclusionsConclusions

Photonics brings together chemists, materials scientists, physicists, and engineers from both academia and industry to create the organic materials for emerging new electronic and photonic technologies.