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Oct. 2, 2013
Light-Driven Molecular Crystal Actuators
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
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
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%
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
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
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
What is a light-driven molecular actuator?
Morimoto M.; Irie M. J. Am. Chem. Soc. 2010, 132,14172-14178. 8
1 mm
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the
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ted
pap
er
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
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
What is atomic force microscopy (afm)?
11
Detector
Scanner
Cantilever
Sample
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
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
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
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
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
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
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
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
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.
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)
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
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
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
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
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.
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
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
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
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.
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.
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.
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
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
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.
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.
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
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
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
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.
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.
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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
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
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.
The crystal spins a gearwheel
45 Terao F.; Morimoto M.; Irie M. Angew. Chem. Int. Ed. 2012, 51, 901 –904.
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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
Acknowledgements
Dr. Jackson
Dr. Xuefei
Dr. Saffron
Dr. Redko
Greg, Jason, Souful, Mahlet, Chao, Fatmata, Darya and Andrew
47
And ...
Thank You For Your Attention