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Tobe LaboratoryKyohei Kaneko
Synthesis of 2D Polymer Using Imine-Forming Reaction on Surfaces
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Contents
• Introduction ・ Concept of 2D Polymer ・ Previous Research Toward The Synthesis of 2D Polymer on Surfaces ・ My Project
• Experimental results ・ STM Observation ・ 1H NMR Experiment
• Summary
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What is 2D Polymer ?
Schlüter, D. et.al. Angew. Chem. Int. Ed. 2009, 48, 1030–1069.
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Chemical Reaction on Surfaces
Gorthelf, K. V.; Linderoth, T. R. et al. Angew. Chem. Int. Ed. 2008, 47, 4406-4410.
= imine bond
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Purpose of My Work
Functional Group
Self-Assembly
Guest Molecule
Chemical Reaction
Covalent Bond
Dehydrobenzo[12]annulene(DBA)
Honeycomb Structure
Self-Assembly
Guest Molecule
Host-Guest Co-adsorption
2D Polymer5
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Previous Work
DBA Core
Benzene Ring
Alkyl Chain
(Vbias = -109 mV, Iset = 402 pA)STM Image of A
Host Molecule
Guest Molecule
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Network Models in This Work
2
Imine–Forming Reaction
Alkyl Chain Interdigitation
Honeycomb Network of DBA 1
Amine Imine Bond
Molecular Network of DBA 1 and Aldehyde 2
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Necessary Requirements for
Synthesis of 2D Polymer
1. DBA derivatives form honeycomb network and functional groups are located at rim of hexagonal pore.
2. Guest molecules are co-adsorbed at hexagonal pores.
3. Chemical reaction between DBA derivatives and Guest molecules proceeds quickly.
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Conditions of STM ObservationConditions
• Solvent: 1-Phenyloctane
1,2,4-Trichlorobenzene
1-Decanol
1-Octanoic Acid• Substrate: Graphite• STM tip was immersed in solution• Negative sample bias• Height image
Sample solution
Graphite
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STM Observation of DBA 1
No Image
× DBA 1 doesn’t form honeycomb structure.
STM Image of DBA 1
● To change in the molecular design● Using another reaction “exchange reaction”
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Exchange Reaction
NnBu
OHCHO
N
nBuHO
3 4 5
stability of imine
N
3
N
nBuHO
5
<
R1O OR2
R2O
R1O OR2
OR1
R1 = C13H27
R2 = (CH2)10O
NH21
R1O OR3
R3O
R1O OR3
OR1
R1 = C13H27
R3 = (CH2)10O
N6
Hydrogen bonding
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STM Observation of DBA 6
STM Image of DBA 6 at 1-phenyloctane/graphiteinterface (Vbias = -162 mV, Iset = 171 pA)
top view
side view
○ DBA 6 forms honeycomb structure.
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STM Observation of DBA 6 and 2
(a) (Vbias = -177 mV, Iset = 398 pA)
STM Image of DBA 6 and 2 at 1-phenyloctane/graphite interface
(b) (Vbias = -177 mV, Iset = 398 pA)
(a)
(b)
○ Guest molecules are co-adsorbed.× Exchange reaction doesn’t proceed.
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Examination of Exchange Reaction with Model Molecules
1 h
2 d
5 d
10 d
11 d
Time1H NMR
of 9
70 ˚C
25 ˚C
13 d
18 d
0.25
0.64
1.38
1.76
2.39
5.44
Intensity of signalHA
1H NMR of exchange reaction between 7 and 8 in C6D6
Integral value is fixed 2.00.
× Exchange reaction proceeds slowly.
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New Molecular Design
R1O OR3
R3O
R1O OR3
OR1
R1 = C13H27
R3 = (CH2)10O
N6
R1O OR4
R4O
R1O OR4
OR1
R1 = C13H27
R4 = (CH2)10O
N10
NN
NN
stability of imine
reactivity of imine
>
<
i-butyl imine
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Examination of Exchange Reaction with Model Molecules
0 h
1 h
8 h
24 h
Time
1H NMR of 9
1H NMR of 11 in CDCl3
0.13
4.38
HA
Intensity of signal
1H NMR of exchange reaction between 11 and 8 in C6D6
○ Exchange reaction proceeds quickly.
Integral value is fixed 2.00.
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Summary• Intense interests have been paid for synthesis and physical properties of 2D
polymer which constitutes ordered nano structure with single atomic film thickness, and which is novel polymeric material.
• In my project, I’ll synthesize 2D polymer via imine formation between the DBA which comprises amino groups at the end of alkyl chains and guest molecule with formyl groups at the ambient condition.
• DBA 1 didn’t form honeycomb network, so I tried to use exchange reaction.
• DBA 6 formed honeycomb network and guest molecule was co-adsorbed, but exchange reaction didn’t proceed.
• With another model molecule which comprised i-butyl imine, exchange reaction proceeded quickly.
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Synthesis of DBA 1
*: 犬飼 晃司 , 2009 年度修士学位論文 , 大阪大学大学院基礎工学研究科19
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Synthesis of Aldehyde 2
*: 太田 雄介 , 2009 年度学士学位論文 , 大阪大学基礎工学部化学応用科学科20
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STM Observation of DBAOC10 and 2
C10H21O OC10H21
C10H21O
C10H21O OC10H21
OC10H21
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Future Work
多孔性二次元ポリマー
分子ふるい、圧力センサー
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Negative Sample Vias
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R eaction M echanism of 13
Oppenauer Oxidation
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Stability of Imine
Aldehyde Amine Molar ratioaldehyde:amine
a)
Imine(%)
K M- 1
4 A 1:3 5.4 2.296 A 1:3 14.0 6.65
CHOOHCHO NH2
4 6 A
Y = yield of imine (%)[R’ NH2]T, [RCHO] T : total concentration
Lehn, J. M. et al. J. Phys. Org. Chem. 2005, 18, 979-985.26