photoactive molecular switches center for supramolecular science department of chemistry françisco...
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Photoactive Photoactive Molecular Molecular SwitchesSwitches
Center for Supramolecular ScienceDepartment of Chemistry
Françisco M. Raymo
SourcesSourcesBooks
Feringa, B. L. (ed.): "Molecular Switches"Wiley-VCH: Weinheim, 2001
Balzani, V.; Venturi, M.; Credi, A.: "Molecular Devices and Machines"Wiley-VCH: Weinheim, 2003
JournalsIrie, M. (ed.): "Photochromism: Memories and Switches"
Chem. Rev. 2000, 100, Issue No. 5
Stoddart, J. F. (ed.): “Molecular Machines”Acc. Chem. Res. 2001, 46, Issue No. 6
ReviewsBalzani, V.; Credi, A.; Raymo, F. M.; Stoddart, J. F.: "Artificial Molecular Machines"
Angew. Chem. Int. Ed. 2000, 39, 3348–3391
Raymo, F. M.: "Digital Processing and Communication with Molecular Switches"Adv. Mater. 2002, 14, 401–414
OutlineOutline
Molecular Switches
Definitions
Classification
Chemical Control
Operating PrinciplesAcid/Base Equilibria
Cation Binding
Electron Transfer
Chemo-Optical Logic GatesFluorescence Modulation
Transmittance Modulation
Supramolecular SwitchesFluorescence Modulation
Optical Control
Operating Principlescis/trans Isomerizations
Ring Opening and Closing
Electron and Energy Transfer
Chemical and Optical ControlAbsorbance Modulation
Fluorescence Modulation
All-Optical Molecular SwitchesAbsorbance Modulation
Fluorescence Modulation
Refractive Index ModulationConclusions
Summary
Comparison of Chemo-Optical and All-Optical Molecular Switches
DefinitionsDefinitions
Input
Switching
High OutputLow Output
What is a molecular switch?
It is a molecular or supramolecular system able to modulate
an output signal in response to an input stimulation!
More DefinitionsMore Definitions
The input and output of a molecular switch can be:Chemical signalsElectrical signalsOptical signals
A molecular switch can have more than:One inputOne outputTwo states
Switching
OutputInput
The states of a molecular switch can be:IsomersAn acid and its conjugated baseDifferent redox states of a moleculeThe complexed and uncomplexed forms of a receptor
Optical OutputsOptical Outputs
Switching
Optical OutputInput
AbsorbanceFluorescence
Refractive Index
ChemicalElectricalOptical
Photoactive molecular switches have optical outputs!
Chemo-OpticalOptical OutputChemical Input
All-OpticalOptical OutputOptical Input
Chemo-Optical SwitchesChemo-Optical Switches
Chemo-OpticalOptical OutputChemical Input
Chemo-OpticalOptical OutputChemical Input 2
Chemical Input 1
Chemo-OpticalOptical OutputOptical Input
Chemical Input
All-Optical SwitchesAll-Optical Switches
All-OpticalOptical OutputOptical Input
Optical OutputOptical Input 2
Optical Input 1
All-Optical
Optical OutputOptical Input 3
Optical Input 2 All-Optical
Optical Input 1
One Chemical InputOne Chemical Input
OutputInput
FluorescenceH+ or M+
The chemical input controls the electron transfer process!
Ene
rgy
D*
Excitation
D*
D
A
ElectronTransfer
D*
Excitation
A*
A
D
ElectronTransfer
Two ExamplesTwo Examples
OutputInput
Fluorescence
H+
de Silva, A.P.; Gunaratne, H.Q.N.; McCoy, C.P. Nature 1993, 364, 42–44
Fluorescence
M+
A Molecular NOT GateA Molecular NOT Gate
HighFluorescence
H+
LowFluorescence
H+
Low
High
Fluorescence
High
Low
The fluorescence is high only if the concentration of H+ is
NOT high!
I
0
1
O
1
0
NOT
The fluorescence is high if the concentration of Na+ OR K+
is high!
Na+
Low
Low
High
High
Fluorescence
Low
High
High
High
K+
Low
High
Low
HighM+
HighFluorescence
A Molecular OR GateA Molecular OR Gate
LowFluorescence
OR
I1
0
0
1
1
O
0
1
1
1
I2
0
1
0
1
Two Chemical InputsTwo Chemical Inputs
Output
Input 1 Input 2
de Silva, A.P.; Gunaratne, H.Q.N.; McCoy, C.P. Nature 1993, 364, 42–44
H+ Na+
Fluorescence
The fluorescence is high only if the concentrations of H+
AND Na+ are high!
H+
Low
Low
High
High
Fluorescence
Low
Low
Low
High
Na+
Low
High
Low
HighH+
HighFluorescence
Na+
A Molecular AND GateA Molecular AND Gate
I1
0
0
1
1
O
0
0
0
1
I2
0
1
0
1
AND
LowFluorescence
Chemo-Optical Logic GatesChemo-Optical Logic Gates
Akkaya et al.Org. Lett. 2000, 2, 1725–1727
NAND
dAMP / dTMP
XOR
H+ / Ca2+
de Silva et al.J. Am. Chem. Soc. 2000, 122, 3965–3966
de Silva et al.J. Am. Chem. Soc. 1999, 121, 1393–1394
NOR
H+ / Zn2+
INH
H+ / O2
Gunnlaugsson et al.J. Am. Chem. Soc. 2001, 123, 12866–12876
Design of A XOR GateDesign of A XOR Gate
Output
Input 1 Input 2
de Silva, A. P.; McClenaghan, N. D. J. Am. Chem. Soc. 2000, 122, 3965–3966
H+
Ca2+
Transmittance
Operating PrinciplesOperating Principles
LowTransmittance
HighTransmittance
Ca2+
H+
HighTransmittance
LowTransmittance
Ca2+
H+
A
390 nm
Ca2+
H+
H+
+Ca2+
AbsorptionSpectra
A Molecular XOR GateA Molecular XOR Gate
The transmittance is high only if the concentration of
either H+ or Ca2+ is high!
H+
Low
Low
High
High
Transmittance
Low
High
High
Low
Ca2+
Low
High
Low
HighH+
Ca2+
Transmittance
I1
0
0
1
1
O
0
1
1
0
I2
0
1
0
1
XOR
A Molecular Half-AdderA Molecular Half-Adder
H+ Transmittance
Ca2+
XOR
The two molecular switches share the same inputs and can
be operated in parallel when dissolved in the same solution!
H+
Fluorescence
AND
Ca2+H+
Transmittance Fluorescence
Half-Adder
The fluorescence is high only if the concentrations of H+
AND Ca2+ are high!
H+
Low
Low
High
High
Fluorescence
Low
Low
Low
High
Na+
Low
High
Low
High
H+
Fluorescence
Ca2+
The AND ComponentThe AND Component
I1
0
0
1
1
O
0
0
0
1
I2
0
1
0
1
AND
A Supramolecular SwitchA Supramolecular Switch
Credi, A.; Balzani, V.; Langford, S. J.; Stoddart, J. F. J. Am. Chem. Soc. 1997, 119, 2679–2681
Input 1
Input 2
Output
The Supramolecular EventThe Supramolecular Event
ElectronDeficient
Component
SupramolecularAssociation
LowFluorescence
ElectronRich
Receptor
HighFluorescence
MechanismMechanism
Electron transfer from the host to the guest quenches the
fluorescence of the macrocyclic receptor!
Low Fluorescence
Ene
rgy
D*
Excitation
D*
D
A
ElectronTransfer
A Chemical InputA Chemical Input
Supramolecular
Association
LowFluorescence
HighFluorescence
BuNH2
The fluorescence is high if the concentration of BuNH2
is high!
Fluorescence
Low
High
BuNH2
Low
High
Another Chemical InputAnother Chemical Input
Supramolecular
Association
LowFluorescence
H+
HighFluorescence
The fluorescence is high if the concentration of H+ is high!
Fluorescence
Low
High
H+
Low
High
The fluorescence is high only if the concentration of either H+ or BuNH2 is high!
H+
Low
Low
High
High
Fluorescence
Low
High
High
Low
BuNH2
Low
High
Low
High
A Supramolecular XOR GateA Supramolecular XOR Gate
I1
0
0
1
1
O
0
1
1
0
I2
0
1
0
1
XOR
Low Fluorescence
H+ BuNH2
BuNH3+
Optical InputsOptical Inputs
Switching Mechanism
cis/trans Isomerization
Ring Opening/Closing Reaction
Electron Transfer
Energy Transfer
Switching
Optical OutputOptical Input
AbsorbanceFluorescence
Refractive Index
ciscis/trans rans IsomerizationsIsomerizations
Dark
1
Azobenzene
Dihydroxychalcone
DihydrochalconesDihydrochalcones
365 nm
0.04 ()
< 1 s
313 nm
0.40 ()
Dark
22 h (t1/2)
Pina, F.; Roque, A.; Melo, M. J.; Maestri, M.; Belladelli, L.; Balzani, V. Chem. Eur. J. 1998, 4, 1184–1191
HighAbsorbanceat 350 nm
LowAbsorbanceat 350 nm
The absorbance can be modulated turning on and off an
optical input!
Fluorescence ModulationFluorescence Modulation
Dark
365 nm
7 (pH)365 nm
Off
Off
On
On
Fluorescence
Low
Low
Low
High
H+
Low
High
Low
High
H+1
Fluorescence
The fluorescence is high only if the optical input is on
AND the concentration of H+ is high!
I1
0
0
1
1
O
0
0
0
1
I2
0
1
0
1
AND
Ring Opening and ClosingRing Opening and Closing
Spiropyran
Dihydroazulene
1
Dark
SpiropyransSpiropyrans
Raymo, F. M.; Giordani, S.; White, A. J. P.; Williams, D. J. J. Org. Chem. 2003, 68, 4158–4169
The absorbance at two different wavelengths can be
controlled with a chemical and two optical inputs!
340 nm
560 nm
or Dark
High Absorbanceat 563 nm
H+
High Absorbanceat 401 nm
Input String Input String 000000
I1
I2
I3
Input Signals
340 nm
560 nm
H+
OFF
0
0
0
ON
O1
O2
Output Signals
Absorbance at 401 nm
Absorbance at 563 nm
OFF
0
0
ON
Input String Input String 100100
I1
I2
I3
Input Signals
340 nm
560 nm
H+
OFF
0
0
ON
1
O1
O2
Output Signals
Absorbance at 401 nm
Absorbance at 563 nm
OFF
0
ON
1
340 nm
HighAbsorbanceat 563 nm
Input String Input String 101101
I1
I2
I3
Input Signals
340 nm
560 nm
H+
OFF
0
ON
1
1
O1
O2
Output Signals
Absorbance at 401 nm
Absorbance at 563 nm
OFF
0
ON
1
340 nm
H+
High Absorbanceat 401 nm
O1 O2I1 I2 I3
Truth Table and Logic CircuitTruth Table and Logic Circuit
0
1
0
0
0
1
0
1
0
0
0
1
0
0
1
0
Output Signals
Absorbanceat 401 nm
Absorbanceat 563 nm
0
0
0
1
0
1
1
1
0
0
1
0
1
0
1
1
0
1
0
0
1
1
0
1
Input Signals
340 nm 560 nm H+
DihydroazulenesDihydroazulenes
Daub, J.; Fischer, C.; Salbeck, J.; Ulrich, K. Adv. Mater. 1990, 2, 366–369
The nature of the substituents affects dramatically the
quantum yield of the photoinduced rearrangement!
0.0004 ()
366 nm
0.40 ()
Dark
4 h (t1/2)
LowAbsorbanceat 468 nm
HighAbsorbanceat 468 nm
411 nm
Absorbance ModulationAbsorbance Modulation
H+
Diederich et al. Helv. Chim. Acta 2001, 84, 743–777
The absorbance is high only if
the optical input is on AND the
concentration of H+ is high!
411 nm
Off
Off
On
On
Absorbance
Low
Low
Low
High
H+
Low
High
Low
High
Absorbance at 500 nm
I1
0
0
1
1
O
0
0
0
1
I2
0
1
0
1
AND
Two Optical InputsTwo Optical Inputs
Diarylethene
Furylfulgide
2
1
DiarylethenesDiarylethenes
517 nm
0.28
313 nm
0.31 () HighAbsorbance at 565 nm
This diarylethene survives 13,000 switching cycles in
aerated hexane!
Matsuda, K.; Irie, M. J. Am. Chem. Soc. 2000, 122, 7195–7201
Fatigue ResistanceFatigue Resistance
>440 nm
0.01
313 nm
0.68 ()High
Absorbance at 565 nm
The concentration of this diarylethene drops to 80% after
80 switching cycles in aerated hexane and after 200
switching cycles in dearated hexane!
Irie, M.; Thorsten, L.; Uchida, K.; Kobatake, S.; Shindo, Y. Chem. Commun. 1999, 747–750
Switching SpeedsSwitching Speeds
The concentration of this diarylethene drops to 80% after
70 switching cycles in aerated hexane and after 480
cycles in dearated hexane!
Miyasaka, H.; Araki, S.; Tabata, A.; Nobuto, T.; Mataga, N.; Irie, M. Chem. Phys. Lett. 1994, 230, 249–254
532 nm
2–3 ps ()
355 nm
8 ps () HighAbsorbance at 560 nm
Refractive Index ModulationRefractive Index Modulation
Diarylethenes can be trapped in polymer matrices!
Tanio, N.; Irie, M. Jpn. J. Appl. Phys. 1994, 33, 3942–3946
n (10–3)
28
15
5
Matrix
Polyolefin
Polymethyl methacrylate
Polyfluoroethyl methacrylate
(nm)
633
633
1300
517 nm
313 nm HighRefractive
Index
LowRefractive
Index
A Mach-Zehnder InterferometerA Mach-Zehnder Interferometer
Ebisawa, F.; Hoshino, M.; Sukegawa, K. Appl. Phys. Lett. 1994, 65, 2919–2921
500 nm
313 nm HighRefractive
Index
LowRefractive
Index
Port 1
Port 2
Port 3
Port 4
Si WaferSiO2•TiO2 Core
P3FMA–MMA Cladding
SiO2•TiO2 CoreDoped P3FMA–MMA Cladding
Time (s)
Pow
er (W
)
Port 3
Port 4
0 8000
100
On
Off
On
Off
313 nm 500 nm
Energy TransferEnergy Transfer
Irie, M.; Fukaminato, T.; Sasaki, T.; Tamai, N.; Kawai, T. Nature 2002, 420, 759–760
488 nm325 nm
*
*
Fluorescence
Electron and Energy TransferElectron and Energy Transfer
Endtner, J. M.; Effenberger, F.; Hartschuh, A.; Port, H. J. Am. Chem. Soc. 2000, 122, 3037–3046
528 nm
350 nm
385 nm385 nm
* *
*High
Absorbanceat 690 nm
R = –(CH)2Me
Electronic MotionElectronic Motion
Lukas, A. S.; Bushard, P. J.; Wasielewski, M. R. J. Am. Chem. Soc. 2001, 123, 2440–2441
Input 2
Input 1
Output
480 nm
HighAbsorbance at 720 nm
420 nm
MechanismMechanism
D*
D
A1*
A1
A2
A3
120 ps
420 nm
420 nm
490 fs
480 nm
480 nm
5 ps
HighAbsorbanceat 720 nm
Ene
rgy
D
A1 A2 A3
An All-Optical AND GateAn All-Optical AND Gate
480 nm
420 nm
HighAbsorbanceat 720 nm
The absorbance is high only if both inputs are applied!
420 nm
Off
Off
On
On
Absorbance
Low
Low
Low
High
480 nm
Off
On
Off
On
I1
0
0
1
1
O
0
0
0
1
I2
0
1
0
1
AND
Chemical Inputs: A SummaryChemical Inputs: A Summary
Optical OutputChemical Input
OpticalOutput
Chemical Input 1 Chemical Input 2
ChemicalInput 1
ChemicalInput 2
Optical Output
Optical Inputs: A SummaryOptical Inputs: A SummaryOpticalInput 1
OpticalInput 2
ChemicalInput
OpticalInput
OpticalOutput
OpticalInput
OpticalOutput
OpticalInput 2
OpticalInput 1
OpticalInput 2
OpticalOutput
OpticalInput 1
Chemo- and All-Optical SwitchesChemo- and All-Optical Switches
Chemo-Optical
Solution
Protonation/DeprotonationComplexation/Decomplexation
Nuclear Motion
Diffusion Limited
Byproduct Accumulation
Chemical Sensing
All-Optical
SolutionPolymer Matrices
cis/trans IsomerizationRing Opening/ClosingElectron/Energy Transfer
Nuclear MotionElectronic Motion
Photodegradation
Optical MemoriesOptical Switches
Medium
Operating Principles
Mechanism
Speeds
Stability
Reversibility
Possible Applications