Fluoropolymer 2014, Oct 14. Shinsuke Inagi. Department of Electronic Chemistry Tokyo Institute of Technology, Japan.

Transcription

1 Fluoropolymer 2014, Oct 14 Shinsuke Inagi Department of Electronic Chemistry Tokyo Institute of Technology, Japan

2 Contents 1. Electrochemical Polymer Reactions Anodic Fluorination, Halogenation Cathodic Hydrogenation Parallel Reactions 2. Bipolar Electrochemistry Gradient Materials Gradient Patternings Electro-click Surface Modification

3 Contents 1. Electrochemical Polymer Reactions Anodic Fluorination, Halogenation Cathodic Hydrogenation Parallel Reactions 2. Bipolar Electrochemistry Gradient Materials Gradient Patternings Electro-click Surface Modification

4 Electrochemical Polymer Reactions Conjugated polymer Dopant Anode Oxidation Reduction Anode (a) Reversible electron transfer

5 Electrochemical Polymer Reactions Conjugated polymer Dopant Anode Oxidation Reduction Anode (a) Reversible electron transfer Boeing 787 Electrochromic window

6 Electrochemical Polymer Reactions Conjugated polymer Dopant Anode Oxidation Reduction Anode Following reaction (b) Electrosynthesis Anode

7 Electrochemical Polymer Reactions Conjugated polymer Dopant Anode Oxidation Reduction Anode Following reaction (b) Electrosynthesis Anode Pickup et al., Chem. Mater. 1996, 8, 701 Belanger et al., Langmuir 2000, 16, 4362 Simonet et al., J. Electroanal. Chem. 1996, 416, 187 Poorly Characterized by EDX and CV

8 Electrochemical Polymer Reactions Conjugated polymer Dopant Oxidation Anode Anode Reduction (a) Reversible electron transfer Following reaction (b) Electrosynthesis Anode Chem. Commun. 2009, 1718 Macromolecules 2009, 42, 3755 Macromolecules 2009, 42, 3881 J. Electrochem. Soc. 2010, 157, E88 Polym. Chem. 2011, 2, 1632 Langmuir 2010, 26, Angew. Chem. Int. Ed. 2013, 52, 6616 Angew. Chem. Int. Ed. 2010, 49, Langmuir 2011, 27, 7158 J. Am. Chem. Soc. 2012, 134, 4034 J. Electrochem. Soc. 2012, 159, G146 ACS Macro Lett. 2012, 1, 656

9 Proof-of-Concept: Fluorination Fluorodesulfurization Solubility, Film-forming ability Electroactive moiety T. Fuchigami et al., J. Electroanal. Chem. 2001, 507, 30. P1: M n = 6400, M w = 19300, M w /M n = 3.0

10 Proof-of-Concept: Fluorination Electrolysis Polymer Synthesis Film Formation Solid-phase Reaction Wash and Purification Characterization S. Inagi, S. Hayashi, T. Fuchigami, Chem. Commun. 2009, 1718

11 Product Well-characterized q a GPC data 0 F/mol q a M n = 6400, M w = 19300, M w /M n = F/mol Without degradation and propagation 24 F/mol M n = 5800, M w = 18300, M w /M n = 3.2 S. Hayashi, S. Inagi, T. Fuchigami, Macromolecules, 2009, 42, 3755

12 n-type Property CV in the film state Poly(dioctylfluorene) P2 S. Hayashi, S. Inagi, T. Fuchigami, Macromolecules, 2009, 42, 3755

13 DFT: Donor-Acceptor Structure D2 HOMO (-5.54 ev) LUMO (-1.53 ev) DFT with B3LYP/6-31G(d,p) method S. Hayashi, S. Inagi, T. Fuchigami, Macromolecules, 2009, 42, 3755

14 Blue Emission in Solution Photoluminescence in CHCl 3 PreP1 P1 P2 S. Hayashi, S. Inagi, T. Fuchigami, Macromolecules, 2009, 42, 3755

15 Current Chlorination Tuning of Electronic Property E onset, ox (V) vs. SCE Octyl Octyl S n -2me, -mh + Et 4 NCl/MeCN (m = 1,2) Octyl Octyl mcl S n 0 F/mol (0.0) (chlorination ratio) F/mol (0.66) F/mol (1.02) 20 F/mol (1.46) E (V) vs SCE Chlorination ratio Control of HOMO level S. Inagi, S. Hayashi, K. Hosaka, T. Fuchigami, Macromolecules 2009, 42, S. Inagi, K. Hosaka, S. Hayashi, T. Fuchigami, J. Electrochem. Soc. 2010, 157, E88.

16 Reductive Hydrogenation O 4e, 4H + H H n -H 2 O C 8 H 17 C 8 H 17 Et 4 NOTs/i-PrOH C 8 H 17 C 8 H 17 n Tuning of LUMO level and fluorescence properties S. Inagi, K. Koseki, S. Hayashi, T. Fuchigami, Langmuir 2010, 26,

17 Twice as Good Parallel Reactions in one pot P-H P-OH P-O In 0.1 M Et 4 NOTs/i-PrOH S. Inagi, H. Nagai, I. Tomita, T. Fuchigami, Angew. Chem. Int. Ed. 2013, 52, 6616.

18 Summary 1 Electrochemical Post-Functionalization Tuning of optoelectronic properties Tailored polymers Quantitative transformation Solid-state electron transfer

19 Summary 1 Electrochemical Post-Functionalization Tuning of optoelectronic properties Tailored polymers Quantitative transformation Solid-state electron transfer What will happen if potential distribution is applied?

20 Contents 1. Electrochemical Polymer Reactions Anodic Fluorination, Halogenation Cathodic Hydrogenation Parallel Reactions 2. Bipolar Electrochemistry Gradient Materials Gradient Patternings Electro-click Surface Modification

21 Bipolar Electrochemistry woche35b/woche35b.html Wireless electrode Anodic and cathodic areas on a surface with a potential gradient

22 Potential Distribution on Bipolar Electrode Electrode system Insulator Insulator Bipolar Electrode Potential slope J. Electrochem. Soc. 2012, 159, G146. Angew. Chem. Int. Ed. 2010, 49, Langmuir 2011, 27, J. Am. Chem. Soc. 2012, 134, 4034.

23 Gradient Chlorination Me -2e, -H + Cl Me S n Et 4 NCl/MeCN S n

24 Gradient Chlorination Me -2e, -H + Cl Me S n Et 4 NCl/MeCN S n Chlorinated As prepared 0.8 V 1.0 V 1.2 V 1.4 V S. Inagi, Y. Ishiguro, M. Atobe, T. Fuchigami, Angew. Chem. Int. Ed. 2010, 49,

25 Site-selective Potential Application Cylinder electrodes Bipolar chlorination of PMT film Y. Ishiguro, S. Inagi, T. Fuchigami, J. Am. Chem. Soc. 2012, 134, 4034.

26 Electro-click Reaction Electrogenerated Cu(I) Larsen, et al., Adv. Mater. 2009, 21, Indirect electrolysis

27 Electro-click Modification Cl N 3 O S O + HO OH Cl p-toluenesulfonic acid Toluene 90 o C, 24 h O S O NaN 3 DMF 120 o C, 3 h O S O 33% 94% EDOT-N 3 reference electrode N 3 N 3 O O Electropolymerization O O S EDOT-N 3 (50 mm) 0.1 M Bu 4 NPF 6 /MeCN Potential sweep method -0.1 ~ +1.6 V (vs. SCE) S n PEDOT-N 3 ITO electrode (0.5 x 2.0 cm 2 )

28 Electro-click Modification U-type cell Bipolar electrode PEDOT-N 3 film Cu(II) Cu(I) S O O n Cu(II) Cathodic surface Anodic surface N R 3 R R R Electro-click reaction S S m n-m O O O O Anode Cathode (Driving electrodes) N R N N N 3 R R

29 Electro-click Modification Cathodic Anodic Cu(II) Cu(I) Cu(II) Electro-click H 2 O/tert-BuOH (2/1) 10 mm CuSO 4 10 mm alkyne Current: 0.50 ma Charge: 30 mc N. Shida, Y. Ishiguro, M. Atobe, T. Fuchigami, S. Inagi, ACS Macro Lett., 2012, 1, 656.

30 Electro-click Modification F/S ratio Cathodic Anodic Cu(II) Cu(I) Cu(II) Electro-click Position (mm) 140 o 129 o 120 o 2 mm 10 mm 18 mm N. Shida, Y. Ishiguro, M. Atobe, T. Fuchigami, S. Inagi, ACS Macro Lett., 2012, 1, 656.

31 Electro-click Modification Cathodic Anodic Cu(II) Cu(I) Cu(II) Triazole Electro-click Azide N. Shida, Y. Ishiguro, M. Atobe, T. Fuchigami, S. Inagi, ACS Macro Lett., 2012, 1, 656.

32 Electro-click Modification Anodic Cathodic Electro-click 10 mm CuSO 4 10 mm propargyl alcohol Current: 0.50 ma Charge: 30 mc 137 o 136 o 84 o 60 o 4 mm 8 mm 12 mm 16 mm N. Shida, Y. Ishiguro, M. Atobe, T. Fuchigami, S. Inagi, ACS Macro Lett., 2012, 1, 656.

33 Gradient -Photoluminescence In 5 mm Et 4 NOTs/i-PrOH Angew. Chem. Int. Ed. 2013, 52, PL under UV-irradiation

34 Summary 2 S. Inagi, T. Fuchigami, Macromol. Rapid Commun. (Feature Article) 2014, 35, 854.

35 Acknowledgment Prof Toshio Fuchigami (Tokyo Tech) Prof Mahito Atobe (Yokohama National Univ) Prof Ikuyoshi Tomita (Tokyo Tech) JSPS MEXT JST

36 Tokyo Institute of Technology (Tokyo Tech)

37 Tokyo Institute of Technology (Tokyo Tech)

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