Synthesis of Conjugated Polymers from Surface Confined Highly Reactive

Butadiyne Derivatives

Tobe labratoryDaichi Ando

O

OH

NHN

N

N

HNN

N

N

IntroductionTopochemical Polymerization

10,12-Nonacosadiynoic acid

Phthalocyanine

STM Tip

Okawa, Y.; Aono, M. J. Am. Chem. Soc. xxxx, xxx, 000-000.

Contents

・ STM ( Scanning Tunneling Microscope )

・ Self-Assembly

・ Radical Polymerization

・ Background and Purpose of my project

STM Observations of Nanostructure

Graphite Surface

Au(111) Surface

1nm

1nm

Ore of Gold （金の原石）

Graphite

STM

PicoSTM (Agilent)

Nanoscope IIIa (Digital Instruments)

@Tobe lab.

5

Scanning Tunneling Microscopy (STM)

e -

V

I

d d

I

Quantum Tunneling d

STM schematic diagram

I = Ve-cd

Tip

Surface: Ag(111)

What’s Self - Assembly ?

Water Droplets on Cold Glass Surface Product of Alum( ミョウバン )

⊿S＞０Intermolecular

InteractionDisorder Order

<

Hydrogen bonding

Self-Assembly

van der Waals interaction

2D nano-architectures are constructed by molecular self-assembly.

+

- -

+

-

+ +

+

- -

+

-

+ +

Heckl, W. M. et al. Single Mol. 2002, 3, 25. Charra, F. et al. Nano Lett. 2006, 6, 1360.

Hydrogen bond

8

Intermolecular interaction-Hydrogen bond-

Lackinger, M.; Griessl, S.; Heckl, W. M.; Hietschold, M.;Flynn, G. W.; Langmuir, 2005, 21, 4984.

Honeycomb( 蜂の巣 )

Intermolecular interaction-Van der Waals interaction-

Van der waals interaction

Bléger, D.; Kreher, D.; Mathevet, F.; Attias, A.-J.; Schull, G.; Huard, A.; Douillard, L.; Fiorini-Debuischert, C.; Charra, F. Angew. Chem. Int. Ed. 2007, 46, 7404–7407.

9

CH

CHH2C

CH2 CHCH2CH2 CH

CHH2C

CH2 CH CH2 CHCH

A B A B

Homlytic Cleavage ( ホモリシス開裂 )

Radical Polymerization ( ラジカル重合 )

Radical

Radical Polymerization

R2

R1

R2

R1

R2

R1

R2

R1R1

R2

R1

R2

R1

R2

R1

R2

Radical

Stylene

Topochemical Polymerization of Butadiyne Derivatives on Surface

Okawa, Y.; Aono, M. J. Chem. Phys. 2001, 115, 2317-2322.

Monomer molecule

Chain propagation

O

OH

R

R

R

R

R

R

R

R

R

R

R

R

R

R

R

R

R

RR

R

e-

e-

Previous ResearchOctaehydrobenzo[12]annulene Derivatives

Polymerization

Octadehydrobenzo[12]annulene (DBA)

Tobe, Y. et al. Chem. Eur. J. 2010, 16, 8319-8328.

5.9 – 6.1 nm

Purpose of This work

external stimuli

C18H17O

C18H17O

OC18H17

OC18H17

C18H17OHO OC18H17

OH

C18H17OHO OC18H17

OHC18H17O

HO

OC18H17

OH

C18H17OHO

OC18H17

OH

OH

OC18H17C18H17OHO

C18H17O

HO

OH

OC18H17

C18H17OHO OC18H17

OH

C18H17OHO OC18H17

OH C18H17OHO OC18H17

OH

C18H17OHO OC18H17

OH

Polymerization

PolyaceneRadical Intermediate

Previous Subject Following Subject

Snowflake Feather of Peafowl

Zebra’s pattern

Heartbeat

What’s Self - Assembly ?

Topochemical Polymerization of Butadiyne Derivatives on Surface

Okawa, Y.; Aono, M. J. Chem. Phys. 2001, 115, 2317-2322.

Monomer molecule

hn

Electronic excitation

Vibration excitation

Addition reaction

Chain propagation

Dehydrobenzo[12]annulene Derivatives

Zhou, Q.; Carrol, P. J.; Swager, T. M. J. Org. Chem. 1994, 59, 1294-1301.

1a: R = C10H21

1b: R = OC12H25

1c: R = OC14H29

1d: R = OC16H33

1e: R = OC18H37

1f: R = OC20H41

Polymerization

Octadehydrobenzo[12]annulene (DBA) 1

1a

Tobe, Y. et al. Chem. Eur. J. 2010, 16, 8319-8328.

5.9 – 6.1 nm

hn or pulse voltage