Post on 25-Dec-2015
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.