Pressure-Induced Polymerization of 24NHBn(Dehydro[24]annulenes) Shimizu-group M1 NAKASE Tomoya 1.
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Transcript of Pressure-Induced Polymerization of 24NHBn(Dehydro[24]annulenes) Shimizu-group M1 NAKASE Tomoya 1.
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Pressure-Induced Polymerization of 24NHBn(Dehydro[24]annulenes)
Shimizu-groupM1 NAKASE Tomoya
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Contents・ Introduction background example of pressure-induced polymerization about 24NHBn(Dehydro[24]annulenes)・ Experiment setting experiment – observe the color change Raman Spectroscopy measure the electrical resistance consequence・ Summary
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Introduction
carbon nanotubes
・ very small size and high strength・ superior electrical and heat conductivity・ various properties from semiconductor to metal etc.
Approach to produce the annular material which can be controlled in 3 dimension structure like CNTs.
my study : 24NHBn(Dehydro[24]annulenes)
expected polymerization
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Sample : 24NHBn(Dehydro[24]annulenes)collaborative research with Rubin Group (UCLA) and Tobe lab
Doesn’t polymerize by heat or UV. (so far)
→What about pressure ?
Control 24NHBn using side chain.
very unstable
Introduction
24NHBn
expected polymerization figure
Mitsuharu Suzuki, et al., ORGANIC LETTERS Vol.12, No.10, 2346-2349 (2010) 4
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Example of pressure-induced polymerization Diiodobutadiyne : 1
Poly-(diiododiacetylene) (PIDA) : 2
Control PIDA using side chain.
Christopher Wilhelm et al., J.AM.CHEM.SOC , 130 , 4415-4420 (2008)
Introduction
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Christopher Wilhelm et al., J.AM.CHEM.SOC , 130 , 4415-4420 (2008)
Introduction
Using DAC in cocrystals of 1 ・ 3transparent and colorless ⇒blue and opaque (at 0.3 GPa)⇒darken to black (further pressure)
Previous work (observe the color change)
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Using Multi Anvil Press in cocrystals of 1 ・ 3
before pressing
3 GPa 6 GPa
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Experimental method ~ Raman Spectroscopy~
Introduction
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anti-Stokes scattering light
Stokes scattering light
Rayleigh scattering light Incident light
Molecular vibrationhu1
hu0
hu0+ hu1
hu0
hu0 - hu1
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Previous work (Raman Spectroscopy)
Christopher Wilhelm et al., J.AM.CHEM.SOC , 130 , 4415-4420 (2008)
(A) 1 ・ 3 before pressing (B)1 ・ 3 after pressing to 2.8 GPa
(C)2 ・ 5 polymer cocrystal
Introduction
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Motivation
・ Investigate whether pressure induce polymerization or not.
・ Investigate behavior of the electrical resistance by pressure.
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setting・ sample: 24NHBn・ Cell : 50 mm (Cu-Be)・ Diamond : 500μm(Run 1,3,4) 1000μm(Run 2) ・ Gasket : SUS310S (Run 1,3,4) Cu-Be (Run2) ・ Pressure medium : Daphne 7373
Experiment Run 1,2,3,4
Purpose : observe the color change and time dependence of color change (Polymerization?)
Daphne
samplegasket
ruby
500 mm
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ambient pressure 0.49GPa 1.81GPa 0.25GPa
According to sample’s color , color change is irreversible reaction.
Run 1
ambient pressure 0.49 GPa 0.66 GPa 0.82 GPa 1.07 GPa
Run 2
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ambient pressure 0.25 GPa 0.25 GPa after Raman 0.41 GPa
after about 50 hours
This color change is due to time passage or Raman laser?!
Run 3
Run 4 (measure time dependence )ambient pressure 0.16 GPa 0.16 GPa 0.52 GPa 0.77 GPa
: 24hours
The color change is observed by time passage!! 12
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Purpose : measure the electrical resistance
sample setting・ sample: 24NHBn・ Cell : 30 mm (Cu-Be)・ Diamond : 550μm・ Gasket : SUS310S
Insulating LayerAlumina Powder
GasketSUS310S
Pt
sample
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ambient pressure 0.44 GPa 1.10 GPa
Ruby 18.25 GPa5.27 GPa 10.71GPa
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Summary・ The color change is observed above about 0.6 GPa. (Polymerization ?)
・ Also, the color change is observed by time passage at about 0.5 GPa.
・ Laser may induce the color change after pressing. ・ The sample is insulator. (~18 GPa) (Electrical resistance is still high.)
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Future work
To identify the black sample,
・ Solid-state NMR ・ TOF-MS
Pistoncylinder
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Example of pressure-induced polymerization Diiodobutadiyne : 1
Poly-(diiododiacetylene) (PIDA) : 2
Crystal structure
1・ 3 cocrystals
1 ・ 4 cocrystalstop
side
Control PIDA using side chain.
Christopher Wilhelm et al., J.AM.CHEM.SOC , 130 , 4415-4420 (2008)
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Previous work of PIDA (color change)・ DACIn cocrystals of 1 ・ 3t ransparent and colorless ⇒blue and opaque (at 0.3 GPa)⇒darken to black (further pressure)
In cocrystals of 1 ・ 4t ransparent and colorless⇒distinct blue from 1 ・ 3 at a single point (at 2.8 GPa) →spread throughout the material⇒darken to black (further pressure)
※Each of the observed color change is irreversible.
Christopher Wilhelm et al., J.AM.CHEM.SOC , 130 , 4415-4420 (2008)
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Previous work of PIDA (Raman Spectroscopy)
Christopher Wilhelm et al., J.AM.CHEM.SOC , 130 , 4415-4420 (2008)
(A) 1 ・ 3 before pressing (B)1 ・ 3 after pressing to 2.8 GPa
(C)1 ・ 4 before pressing (D)1 ・ 4 after pressing to 3 GPa
(E)2 ・ 5 polymer cocrystal
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X-ray Diffraction Studies1 ・ 3 cocrystals→The sample still contains monomer. (to 1 GPa , blue)
→The mosaicity of the crystal is too big to prevent further analysis.
1 ・ 4 cocrystals→no evidence for polymerization (to 3 GPa , blue)
The black material (1 ・ 3 and 1 ・ 4) doesn’t diffract as a single crystal.
Pressure