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Pressure-Induced Polymerization of Dehydro [24] annulenes Derivative

Pressure-Induced Polymerization of Dehydro [24] annulenes Derivative. Shimizu-group M1 NAKASE Tomoya. 1. Contents. ・ Introduction background about 24NHBn( Dehydro [24] annulenes derivative) example of pressure-induced polymerization ・ Experiment setting

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Pressure-Induced Polymerization of Dehydro [24] annulenes Derivative

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  1. Pressure-Induced Polymerization of Dehydro[24]annulenes Derivative Shimizu-group M1 NAKASE Tomoya 1

  2. Contents ・Introduction background about 24NHBn(Dehydro[24]annulenes derivative) example of pressure-induced polymerization ・Experiment setting experiment – Optical observation Raman Spectroscopy Infrared Spectroscopy mass spectrometry (LDI-TOF) measure the electrical resistance Result & Discussion ・ Summary 2

  3. Introduction ・very small size and high strength ・superior electrical and heat conductivity ・various properties from semiconductor to metal etc. carbon nanotubes synthesis of conjugated tubular structure pressure self-assembly molecule expected polymerization Dehydro[24]annulenes 3

  4. Sample : 24NHBn(Dehydro[24]annulenesderivative)collaborative researchwith Rubin Group (UCLA) and Tobe lab 24NHBn 24NHBn on ambient pressure Doesn’t polymerize by heat or UV. (so far) →What about pressure ? Control 24NHBn using side chain Mitsuharu Suzuki, et al., ORGANIC LETTERS Vol.12, No.10, 2346-2349 (2010) 4

  5. Example of pressure-induced polymerization Diiodobutadiyne : 1 Poly-(diiododiacetylene) (PIDA) : 2 Control PIDA using side chain. 5 Christopher Wilhelm et al.,J.AM.CHEM.SOC , 130 , 4415-4420 (2008)

  6. Previous work • Optical observation • Using Multi Anvil Press in cocrystals of 1 ・ 3 3 GPa 6 GPa before pressing • Raman Spectroscopy (A) 1・3 before pressing (B)1・3 after pressing to 2.8 GPa (C)2・5 polymer cocrystal Christopher Wilhelm et al., J.AM.CHEM.SOC , 130 , 4415-4420 (2008) 6

  7. Motivation The carbonnanotubessynthesis methodhas notbeen developedyet completely in the handling on diameter, length, bond type etc. carbon nanotubes synthesis of conjugated tubular structure pressure self-assembly molecule in crystal 7

  8. Experiment~ strategy~ Raman Spectroscopy mass spectrometry (LDI-TOF) Optical observation Electrical resistance measurement Infrared Spectroscopy 8

  9. sample setting (DAC) Electrical resistance measurement Optical observation Electrode (Pt) Gasket (SUS310s) Insulating Layer (Alumina Powder) Pressure marker (ruby) Powder like sample 500 mm 550μm Sample Pressure medium (Daphne 7373, MeOH) 9

  10. Measure pressure medium dependence 1.70 GPa ambient pressure 0.60 GPa 1.26GPa 1.62GPa sample size: 130×50μm2 24NHBn Pressure medium : Daphne 7373 0.66GPa ambient pressure 0.49 GPa 0.82GPa 1.07GPa sample size: 80×40μm2 The color change depends on the pressure medium. This result supports that expected polymerization will progress. 10 Pressure medium : MeOH

  11. Raman spectroscopy Pressure medium : Daphne 7373 24NHBn 0.41 GPa diamond before pressing 11

  12. Infrared spectroscopy~ supported by Prof. Mita ~ 24NHBn after pressing (recalled sample) C=C伸縮, C=O伸縮 C≡C伸縮 before pressing Sample after the change in color takes a different binding mode. 12

  13. Mass spectrometry (LDI-TOF) ~ supported by Tobe lab ~ 100 before pressing monomer After applying pressure, the signals of monomer reduce. Polymerization?? 5000 1000 1000 2000 2000 2500 2500 500 500 1500 1500 3000 3000 3500 3500 4000 4000 4500 4500 Mass/Charge 100 after pressing (recalled sample) 13 5000 Mass/Charge

  14. Electrical resistance measurement 1.10 GPa 0.44 GPa ambient pressure Ruby 18.25 GPa 5.27 GPa 10.71GPa 14

  15. Summary ・24NHBn seems to polymerize by pressure. - sample color : yellow → black - Expected polymerization will progress. 24NHBn 15

  16. Experimental method ~ Infrared Spectroscopy~

  17. Example ofpressure-induced polymerization Diiodobutadiyne : 1 Poly-(diiododiacetylene) (PIDA) : 2 Crystal structure side １・3cocrystals top Control PIDA using side chain. 1・4 cocrystals Christopher Wilhelm et al.,J.AM.CHEM.SOC , 130 , 4415-4420 (2008)

  18. Previous work of PIDA(color change) ・DAC In cocrystals of 1・3 ｔransparent and colorless ⇒blue and opaque (at 0.3 GPa) ⇒darken to black (further pressure) In cocrystals of 1・4 ｔransparent 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)

  19. Previous work of PIDA (Raman Spectroscopy) (A) 1・3 before pressing (B)1・3 after pressing to 2.8 GPa (D)1・4 after pressing to 3 GPa (C)1・4 before pressing (E)2・5 polymer cocrystal Christopher Wilhelm et al.,J.AM.CHEM.SOC , 130 , 4415-4420 (2008)

  20. X-ray Diffraction Studies 1・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

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