light-driven molecular crystal actuators · 2013. 10. 3. · 2009, 131, 6890-6891. evolution ......
TRANSCRIPT
![Page 1: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/1.jpg)
Oct. 2, 2013
Light-Driven Molecular Crystal Actuators
![Page 2: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/2.jpg)
Overview
Importance of solar energy harvesting
Reversible surface morphology change
Reversible microcrystal shape change
Reversible bending of microcrystals
Reversible bending of composites that contain tiny crystals
Irreversible bending of macrocrystals
Reversible bending of macrocrystals
2
![Page 3: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/3.jpg)
Primary energy demand is growing with population and the population is growing rapidly
Key World Energy Statistics, 2012. www.worldbank.org 3
Mill
ion
to
n o
il e
qu
ival
en
t Primary energy supply
![Page 4: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/4.jpg)
The primary energy source has been mostly fossil fuels
4 Key World Energy Statistics, 2012.
Mtoe: Million ton oil equivalent
1973 2010
Coal/peat
Oil
Natural gas
Coal/peat
Oil
Natural gas
6,107 Mtoe 12, 717 Mtoe
Nuclear
Hydro Biofuels
And waste Renewable 0.9%
Nuclear
Hydro
Biofuels And waste
Renewable 0.1%
![Page 5: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/5.jpg)
Burning fossil fuels should be decreased
Petitto L. A.; Holowka S.; Sergio L. E.; Ostry D. Nature, 2001, 413, 35-36. ELLIS E.C. Science, 2008, 320, 1587-1587. 5
Next generations Pollution
![Page 6: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/6.jpg)
Renewable energy sources need to grow
Schiermeier Q.; Tollefson J.; Scully T.; Witze A.; Morton O.; Nature, 2008, 454, 816-823. 6
Wind Solar
Geothermal
![Page 7: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/7.jpg)
Solar energy harvesting
Shah A.; Torres p.; Tscharner R.; Wyrsch N.; Keppner H. Science, 1999, 285, 692-698. Roeb M.; Müller-Steinhagen H. Science, 2010, 329, 773-774.
Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178.
Solar heating
Solar cells
Artificial photosynthesis
…
Light-driven molecular crystal actuators
7
![Page 8: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/8.jpg)
What is a light-driven molecular actuator?
Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. 8
1 mm
This
imag
e is
th
e f
irst
fra
me
of
a vi
de
o t
hat
co
uld
b
e f
ou
nd
in t
he
su
pp
ort
ing
info
rmat
ion
of
the
ci
ted
pap
er
![Page 9: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/9.jpg)
Evolution of light-driven molecular crystal actuators
Reversible surface morphology change
Reversible microcrystal shape change
Reversible bending of microcrystals
Reversible bending of composites that contain tiny crystals
Irreversible bending of macrocrystals
Reversible bending of macrocrystals
9
![Page 10: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/10.jpg)
Solid phase photoinduced isomerization
Irie M.; Kobatake S.; Horichi M. Science, 2001, 291, 1769-1772. 10
Surface A
Surface B
116° 116°
1.0 mm
λ=366 nm
λ> 500 nm
Open ring Closed ring
![Page 11: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/11.jpg)
What is atomic force microscopy (afm)?
11
Detector
Scanner
Cantilever
Sample
![Page 12: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/12.jpg)
Reversible steps and valleys form on two faces of the crystal
12
Surface A
Surface B
before UV irradiation after UV Irradiation after visible irradiation
Surface A
Surface B
116°
Irie M.; Kobatake S.; Horichi M. Science, 2001, 291, 1769-1772.
λ=366 nm
λ> 500 nm
![Page 13: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/13.jpg)
Longer irradiation time forms more 1 nm height steps on surface A
13 Irie M.; Kobatake S.; Horichi M. Science, 2001, 291, 1769-1772.
Surface A
![Page 14: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/14.jpg)
Comparison of closed and open-ring isomers shows a considerable molecular shape change upon isomerization
1.41 nm
0.49 nm 0.39 nm
1.39 nm
14 Irie M.; Kobatake S.; Horichi M. Science, 2001, 291, 1769-1772.
λ=366 nm
λ> 500 nm
![Page 15: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/15.jpg)
Molecular shape change results in crystal deformation
Surface A
Surface B
116°
b
c c
a
β
1.0 nm
Irie M.; Kobatake S.; Horichi M. Science, 2001, 291, 1769-1772.
1.41 nm
0.49 nm
15
![Page 16: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/16.jpg)
Evolution of light-driven molecular crystal actuators
Reversible surface morphology change
Reversible microcrystal shape change
Reversible bending of microcrystals
Reversible bending of composites that contain tiny crystals
Irreversible bending of macrocrystals
Reversible bending of macrocrystals
16
![Page 17: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/17.jpg)
Reversible single to single crystal transformation accompanied with crystal deformation
Kobatake S.; Takami S.; Muto H.; Ishikawa T.; Irie M. Nature, 2007, 446, 778-781.
10 µM 10 µM
17
λ=365 nm
λ> 500 nm
![Page 18: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/18.jpg)
As the reaction proceeds, the tension increases in the lattice
18
10 µM 10 µM
θ (
°)
Absorbance at 600 nm
Kobatake S.; Takami S.; Muto H.; Ishikawa T.; Irie M. Nature, 2007, 446, 778-781.
Ab
sorb
ance
Wavelength/nm
λ=365 nm
λ> 500 nm
![Page 19: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/19.jpg)
The solid phase conversion is 70% under photostationary state
Ab
sorb
ance
Wavelength/nm
Kobatake S.; Takami S.; Muto H.; Ishikawa T.; Irie M. Nature, 2007, 446, 778-781.
19
10 µM 10 µM
λ=365 nm
λ> 500 nm
![Page 20: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/20.jpg)
Crystal packing explains the crystal shape change
20
A. Open-ring B. closed-ring after irradiation
C. Closed-ring crystalized from solution
Kobatake S.; Takami S.; Muto H.; Ishikawa T.; Irie M. Nature, 2007, 446, 778-781.
![Page 21: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/21.jpg)
Single crystals have Fast response time
Each frame is 25 micro second
21 Kobatake S.; Takami S.; Muto H.; Ishikawa T.; Irie M. Nature, 2007, 446, 778-781.
1 2 3 4 5 6
355 nm (8 ns)
![Page 22: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/22.jpg)
Evolution of light-driven molecular crystal actuators
Reversible surface morphology change
Reversible microcrystal shape change
Reversible bending of microcrystals
Reversible bending of composites that contain tiny crystals
Irreversible bending of macrocrystals
Reversible bending of macrocrystals
22
![Page 23: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/23.jpg)
Azo-dye crystals bend reversibly
Koshima H.; Ojima N.; Uchimoto H. J. Am. Chem. Soc. 2009, 131, 6890-6891. 23
λ=365 nm
heat
UV
20 μm
a
a b
c a
![Page 24: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/24.jpg)
What is X-ray diffraction (XRD)?
X-ray source
Crystaline sample
2θ
2θ
Bragg’s law nλ=2dSinθ
24
d
inte
nsi
ty (
cps)
2θ (degree)
Detector
θ
![Page 25: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/25.jpg)
The crystal deforms reversibly
25
inte
nsi
ty (
cps)
2θ (degree)
rela
tive
inte
nsi
ty, %
Time (s)
UV stop
UV 5 s
inte
nsi
ty (
cps)
2θ (degree)
Koshima H.; Ojima N.; Uchimoto H. J. Am. Chem. Soc. 2009, 131, 6890-6891.
After irradiation Before irradiation
![Page 26: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/26.jpg)
Around 1% of molecules react in solid phase
after 30 minutes
2.35
2.23
26 Koshima H.; Ojima N.; Uchimoto H. J. Am. Chem. Soc. 2009, 131, 6890-6891.
![Page 27: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/27.jpg)
Evolution of light-driven molecular crystal actuators
Reversible surface morphology change
Reversible microcrystal shape change
Reversible bending of microcrystals
Reversible bending of composites that contain tiny crystals
Irreversible bending of macrocrystals
Reversible bending of macrocrystals
27
![Page 28: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/28.jpg)
Crystal phase salicylideneaniline isomerization
Harada J; Uekusa H; Ohashi Y. J. Am. Chem. Soc. 1999, 121, 5809-5810. 28
λ=730 nm λ= 530 nm
![Page 29: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/29.jpg)
HNAN crystals dispersed in PVDF–HFP forms composites that bend reversibly upon UV illumination
Lan T.; Chen W. Angew. Chem. Int. Ed. , 2013, 52, 6496-6500.
2-hydroxynaphthylidene-1’-naphthylamine (HNAN)
Polyvinylidene fluoride–hexafluoropropylene (PVDF–HFP)
dark
29
λ=360 nm
75 mm x 25 mm x 52 μm
Ave
rage
dis
pla
cem
ent/
mm
g
HNAN mass percentage
![Page 30: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/30.jpg)
The bending is reversible and relatively strong
30
cycle
Dis
pla
cem
ent
/ m
m
Lan T.; Chen W. Angew. Chem. Int. Ed. , 2013, 52, 6496-6500.
![Page 31: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/31.jpg)
The direction of bending depends on the concentration gradient direction of HNAN in the composite
31
10 μm
count
2 μm
cou
nt
included angle (°)
Lan T.; Chen W. Angew. Chem. Int. Ed. , 2013, 52, 6496-6500.
![Page 32: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/32.jpg)
HNAN crystals are responsible for bending
32
time/s
dis
pla
cem
ent/
μm
2θ (°)
HNAN
PVDF–HFP
composite
Lan T.; Chen W. Angew. Chem. Int. Ed. , 2013, 52, 6496-6500.
1. Large single crystals of HNAN responds to light:
2. XRD shows that HNAN is crystalline in the composite:
3. PVDF-HFP does not respond to light.
![Page 33: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/33.jpg)
Evolution of light-driven molecular crystal actuators
Reversible surface morphology change
Reversible microcrystal shape change
Reversible bending of microcrystals
Reversible bending of composites that contain tiny crystals
Irreversible bending of macrocrystals
Reversible bending of macrocrystals
33
![Page 34: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/34.jpg)
π–π interactions and hydrogen-bondings increase the flexibility
Sun J.; Li W.; Chen C.; Ren C.; Pan D.; Zhang J. Angew. Chem. Int. Ed. , 2013, 52, 6653-6657.
3.745 Å
3.499 Å
3.745 Å
3.647 Å
3.601 Å
3.601 Å
34
![Page 35: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/35.jpg)
Highest flexibility ever seen among macroscopic crystals
35
1 mm
Sun J.; Li W.; Chen C.; Ren C.; Pan D.; Zhang J. Angew. Chem. Int. Ed. , 2013, 52, 6653-6657.
![Page 36: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/36.jpg)
Contraction of on one side of the crystal bends the crystal towards itself
36 Sun J.; Li W.; Chen C.; Ren C.; Pan D.; Zhang J. Angew. Chem. Int. Ed. , 2013, 52, 6653-6657.
![Page 37: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/37.jpg)
Evolution of light-driven molecular crystal actuators
Reversible surface morphology change
Reversible microcrystal shape change
Reversible bending of microcrystals
Reversible bending of composites that contain tiny crystals
Irreversible bending of macrocrystals
Reversible bending of macrocrystals
37
![Page 38: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/38.jpg)
Macro crystals bend reversibly
38 Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178.
λ=365 nm from right
side
λ>440 nm From right
side
1 mm
![Page 39: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/39.jpg)
Electrocyclic reaction increases the height of the molecule
39
b
a
H: 0.534 nm H: 0.679 nm
B: 1.411 nm B: 1.554 nm
Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178.
λ= 365 nm
λ> 440 nm
![Page 40: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/40.jpg)
Molecular geometry change increases the surface area on one side of the crystal and bends it away
40
UV
UV
b
a
c
b
Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178.
![Page 41: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/41.jpg)
A 0.17 mg piece of crystal pulls up 46.77mg of a lead ball
41 Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178.
This
imag
e is
th
e f
irst
fra
me
of
a vi
de
o t
hat
co
uld
b
e f
ou
nd
in t
he
su
pp
ort
ing
info
rmat
ion
of
the
ci
ted
pap
er
![Page 42: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/42.jpg)
A cocrystal of two similar diarylalkenes bends towards light
42 Terao F.; Morimoto M.; Irie M. Angew. Chem. Int. Ed. 2012, 51, 901 –904.
A B
100 % pure A
A:B 37:63
λ= 365 nm
![Page 43: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/43.jpg)
The crystal works reversible
43 Terao F.; Morimoto M.; Irie M. Angew. Chem. Int. Ed. 2012, 51, 901 –904.
1st cycle 500th cycle 1000th cycle
0.5 mm
cycle number
tip
dis
pla
cem
ent
/mm
![Page 44: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/44.jpg)
The crystal bends under water remotely
UV Vis.
1 mm
44 Terao F.; Morimoto M.; Irie M. Angew. Chem. Int. Ed. 2012, 51, 901 –904.
![Page 45: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/45.jpg)
The crystal spins a gearwheel
45 Terao F.; Morimoto M.; Irie M. Angew. Chem. Int. Ed. 2012, 51, 901 –904.
This
imag
e is
th
e f
irst
fra
me
of
a vi
de
o t
hat
co
uld
b
e f
ou
nd
in t
he
su
pp
ort
ing
info
rmat
ion
of
the
ci
ted
pap
er
![Page 46: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/46.jpg)
Conclusions
Molecular crystals can convert light to mechanical motion
Small sized crystals are able to result in macroscopic motion if they are used in composites
Inter molecular interactions could be established by molecular design
Additives can increase the strength and flexibility of the crystal
46
![Page 47: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/47.jpg)
Acknowledgements
Dr. Jackson
Dr. Xuefei
Dr. Saffron
Dr. Redko
Greg, Jason, Souful, Mahlet, Chao, Fatmata, Darya and Andrew
47
![Page 48: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/48.jpg)
And ...
Thank You For Your Attention
![Page 49: Light-Driven Molecular Crystal Actuators · 2013. 10. 3. · 2009, 131, 6890-6891. Evolution ... 1.554 nm Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. λ= 365 nm](https://reader035.vdocuments.us/reader035/viewer/2022071506/6126a7160f9f353a963d656a/html5/thumbnails/49.jpg)