Photochromism - Fundamentals and Applications
Transcript of Photochromism - Fundamentals and Applications
Masahiro Irie
Photochromism
- Fundamentals and Applications -
Department of Chemistry and Biochemistry Kyushu University, Fukuoka, Japan
Photon
Energy
Information
Photosynthesis
Photoresponsiveness
Vision
Phototaxis
Phototropism
Photochromism
A Bhν
hν’ Photoreceptor : Rhodopsin (Chlamydomonas)BacteriorhodopsinPhytochromeSodaliteMineral :
Natural
Artificial
Dyes : Spirobenzopyran, Azobenzene・・・
Matel-oxide GlassChalcogenide Glass
XX
Y Y
514 nm
366 nm
300 350 400 450 500 550 600
λ / nm
Abs
orba
nce
0.4
0.3
0.2
0.1
I I I I I I
II
II
N
H3C CH3
O NO2
RN
H3C CH3
NO2
OR
NNN
N
H3C
OO
CH3
CH3
O
OO
OCH3
OO
CH3
CH3H3C CH3H3C
SS
CH3
S
CH3
S
-+
CH3CH3
H3C
F2
F2F2F2F2
F2
OO
1867 M. Fritsche
hν, O2
∆
OCl
Cl
1899 W. Marckwald
ClCl
Cl
Cl
O
Cl
hν+ Cl
∆
(G. Scheibe et al. J. Phys. Chem. 66, 2449 (1962))
Brief History of Photochromism
N OMe
Me Me
N OMe
(J. Chem. Soc., 4522 (1952))
Me Me
1952 E. Fischer, Y. Hirsberg
hν
∆
Self-developing, Dry Photographic Systems
High-speed Printing Materials
Chemical Computer
Camouflage Fabrics
N C R (Spiropyran)R C A (Indigos)American Cyanamid (Spiropyrans, MetalDithizonates)
EG & G (Triarylmethane Leuco Derivatives)Fuji Film (Spiropyrans)
Lack of fatigue resistant characteristics
1970 ~ 1980 Dark Ages
(photo-degradation)
"Photochromism" G. Brown Ed.
N O
N
Me
Me Me
N O
N
Me
Me Me
O
O
Me
Me
MeMe
O
O
Me
OOMe
Fatigue Resistant Spironaphthoxazine
O
O
hν
Me
Thermally Irreversible Compounds
Me
Me Me
1980 ~ Present Renaissance
hν
hν'
∆
NN
N NAzobenzene
hν
hν', ∆
N
H3C CH3
O NO2R
N
H3C CH3
R
NO2
-O
Spirobenzopyran
+hν
hν', ∆
OO
Naphthopyran
hν
hν', ∆
Name Reaction
S S
O O
S
OS
OThioindigo
hν
hν', ∆
Anthracene Dimerhν
hν', ∆
NCCN
NO2
CN
CN
NO2
hν
hν', ∆
Dihydroazulene
Name Reaction
CH3
H3CS S H3C
CH3
S S
Diarylethene
hν'
hν
F2F2 F2
F2F2
F2
H3C
OO
CH3
CH3
O
O O
OCH3
OO
CH3
CH3H3C CH3 H3C
H3Chν'
Furyl Fulgide
hν
O
O O
R
O
O O
R
Naphthacene quinone
hν
hν'
S
O
S
CH3OH3CCH3
CH3
Stilbene Derivative
hν
hν'
Requirements for Photonics Devices
1. Thermal stability of both isomers
2. Fatigue resistant character: repeatable cycle number > 104
3. High sensitivity:quantum yield > 0.5
4. Rapid response
5. Reactivity in the solid state
A Bhν
hν’
A New Class of Photochromic CompoundsThermally Irreversible and Fatigue Resistant
Diarylethenes
R1R2
YR3 R6X R4
R5
R1R2
YR3 R6X R4
R5HH HH
H
H
,
,,:
,,:
,
O O O OO N
CH2CN
SR1
R2
YR3 R3X R1
R2
Me
Me
Me MeS N Me
Me
S OEt NMe
Me
MeO
Me
Me
NC S
F2F2
F2
,
・Both isomers are thermally stable
long term stability :
short term stability : 150 °C
・Low fatigue
repeatable cycle number : 105
・High sensitivityquantum yield : 0.1 -1.0
・Rapid response< 10-11 sec
・Reactivity in the crystalline phase
・Sensitivity at visible region
forward reaction : 488 nmbackward reaction : 780 nm
470,000 years at 30 °C
R2 R5
R3 R6
X Y
R1
R4
hν
hν' R4
R1
YXR6R3
R5R2
Molecular Design of Diarylethenes
Thermal Stability
Fatigue Resistant Character
Response Time
Molecular Orbital Calculation
• Thermal reaction - - - disrotatory mode
A B C D A
B C
D
• Photochemical reaction - - - conrotatory mode
A B C D
A
B
C
D
Conrotatory Mode - - - Photochemical Reaction Process
OO
O O
A ( 50,46 )A ( 48,48 )B ( 49,47 )B ( 43,41 )
A ( 42,42 )
A ( 12,42 )
A ( 12,42 )
B ( 43,41 )
A ( 44,40 )
A ( 48,48 )A ( 50,46 )
B ( 49,47 )
A ( 50,46 )
A ( 48,48 )
A ( 42,42 )
Molecular Design PrincipleThermal Irreversibility
“ When the compound has aryl groups with low aromatic stabilization energy, both isomers of the diarylethene are thermally stable.”
Stable Unstable
OOS S N N
>>> >
φs = 0.001 (φB→A = 1)
A B1 - φsφs
φB→AP
After 103 cyclesAfter 103 cycles
[A] ~ 0.37 [A]0
φs = 0.0001 (φB→A = 1)
After 104 cycles
[A] ~ 0.37 [A]0
S
CH3
H3C S
S
CH3
H3C S
H3C CH3
H3C CH3S
CH3
H3C S
S
CH3
H3C S
> 100,000 > 10,000 ~ 2,000
~ 200 ~ 80
Crystalline Systems
F2
F2
F2
F2
F2
F2
F2 F2
F2 F2
F2 F2
Molecular Design PrincipleFatigue Resistant Character
UV
Vis.
Dichroism
SSH3C
CH3
CH3S
CH3
CH3 SH3C CH3 CH3
F2F2F2
F2F2F2
J. Am. Chem. Soc. 121, 2380 (1999)
SS
CH3
CH3S
CH3
CH3 SO2N NO2 O2N NO2
F2
F2
F2F2
F2F2
J. Am. Chem. Soc. 121, 8450 (1999)
F2F2 F2
SS EtEt
2a
F2F2 F2
SS MeMeF
F
FF
F FF
F
FF
1a
F2F2 F2
SS EtEt
2b
F2F2 F2
SS Me
MeFF
FF
F FF
F
FF
1b
UV
Vis.
UV
Vis.
Photochem. Photobio. Sci. 2,1088 (2003)Chem. Rec. 4, 23 (2004)
Nano-layered Structure
SSH3C
CH3
CH3S
CH3
CH3SH3C CH3 CH3
F2
F2F2
F2F2
F2
X-ray Crystallographic Analysis
1a 1b
J. Am. Chem. Soc. 122, 1589 (2000)
Bull. Chem. Soc. Jpn. 73, 2179 (2000)
4.0 4.5 5.0 5.53.53.02.5Distance between the reacting carbon atoms / A
Φ
0
0.2
0.4
0.6
0.8
1.0
S SR
R
F2F2
F2
Me or H H or Me
R' R'
S SMe
Me
F2F2
F2
R R
S SMe
Me
F2F2
F2
R1 R1
R2R2
Chem. Commun. 2804 (2002)J. Phys. Chem. A. 106, 209 (2002)
SS
CH3
H3CS
CH3
H3C S
F2
F2 F2F2F2
F2
H3C CH3 H3C CH3
Surface Morphology Changes of Single Crystal 1
Science, 291, 1769 (2001)
UV
Vis.
(100)
R6XR3
XR4
R1R2 R5
(R,R) (S,S)
R3X R6
XR1
R4R5R2hν
hν', ∆
+R6
XR3X R4
R1R2 R5
Absolute Asymmetric Photosynthesis
Ang. Chem. 42, 1636 (2003)
Tetrahedron Lett. 42, 7291 (2001)
J. Am. Chem. Soc. 122, 9631 (2000)