Compounds I synthesized in the past.

Postdoctoral Synthesis.

O O

O O

n

PPE1

OC10H21

I I

OC10H21

H21C10O

+

OC10H21

H21C10O

H H + O

O

I

H21C10O

OC10H21

OC10H21

OC10H21

H21C10O

Si Si I OH

OH

HO

II

O(CH2)11OH

HO11(CH2)O

II + Fe

Cl

O

O(CH2)11O

O11(CH2)O

II

Fe

Fe

O

O

+

OC10H21

H21C10O

H H I+

n

OC10H21

H21C10O

O

O H21C10O

OC10H21( )10

( )10

OCH3

OCH3

OCH3

OCH3

I

I

Fe

O

O

Fe

O

O

PPE2

O

OO

O O

O

1

OH

OH

O

O

O

O

I

I+

OC10H21

H21C10O

H H

OC10H21

H21C10O

O

O

O

n

OC10H21

O

+ O

O

I

H21C10O

PPE3

O O

Scheme 1. Synthesis of poly (para-phenyleneethynylene)s.

S Br STMS S

II

OC6H13

H13C6O

I

OC6H13

H13C6O

TMS

S

OC6H13

H13C6O

TMS

S

OC6H13

H13C6O

S

OC6H13

H13C6O

TMSI

S

OC6H13

H13C6O

TMSH2

S

OC6H13

H13C6O

HH2

S

OC6H13

H13C6O

TMSI2

S

OC6H13

H13C6O

TMSH4

2

Br I Br TMS I TMS

TMSS

S

TMSSI

STMS

H 2 SH

H 2

. Scheme 2. Synthesis of oligo [(para-phenyleneethynylene)-alt-(2,5-thienyleneethynylene)]s.

Br I Br TMS

I TMS

TMSBr

Br

2TMSI2

TMSH3

HH3

Scheme 3. Synthesis of oligo (para-phenyleneethynylene)s.

3

S+ NI

SN

SN

I

S+ NI

SN

SN

I

OC6H13

H13C6O

OC6H13

H13C6O

OC6H13

H13C6O

Scheme 4. Synthesis of short molecular wire with pyridyl.

4

NH

N

HN

N

NH

I

I I

I

IH

ON

N

N

N

I

I I

I

Zn

NH

TMSO

HN

HN

N

NH

SMT TMS

SMT TMS

N

N

N

N

SMT TMS

SMT TMS

Zn

N

N

N

N

ZnN

HN

N

NH

NH

+ N

HN

N

NH

H

OTMS

SMT TMS

TMSSMT

N

N

N

N

N

N

N

N

SMT TMS

TMSSMT

Zn

ZnN

HN

N

NH

+

+

Scheme 5. Synthesis of porphyrin derivatives.

5

N

N

N

N

Zn +SI

TMS

H13C6O

OC6H13

N

N

N

N

Zn

S

H13C6O

OC6H13

S

H13C6O

OC6H13

S

OC6H13

H13C6O

S

OC6H13

H13C6O

N

N

N

N

Zn

S

H13C6O

OC6H13

S

H13C6O

OC6H13

S

OC6H13

H13C6O

S

OC6H13

H13C6O

SMT TMS

TMSSMT

N

N

N

N

Zn +SI

N

N

N

N

Zn

S

TMS

S

SMT

S

SMT

S

TMS

TMS

Scheme 6. Synthesis of cross-shaped π–conjugated meso-alkynyl porphyrin derivatives.

6

N

N

N

N

I TMS

OC6H13

H13C6O

OC6H13H13C6O OC6H13

H13C6O

OC6H13

H13C6O

N

N

N

N

Zn +

TMSSMT

SMT TMS

N

N

N

N

OC6H13H13C6O OC6H13

H13C6O

OC6H13H13C6O

Zn Zn

H13C6OOC6H13

H13C6OOC6H13

N

N

N

N

I TMS

OCH3

H3CO

OCH3H3CO OCH3

H3CO

OCH3H3CO

N

N

N

N

Zn +

TMSSMT

SMT TMS

Zn

H3COOCH3

Scheme 7. Synthesis of π–conjugated meso-alkynyl porphyrin derivatives.

7

S

OC6H13

H13C6OI

N

N

N

N

+ TMS

N

N

N

N

S

S

S

S

H13C6OOC6H13

OC6H13H13C6O

N

N

N

N

S

S

S

S

H13C6OOC6H13

OC6H13C6H13O

SMTTMS

SMT

TMS

Zn

ZnZn

OC6H13

H13C6O

H13C6O

OC6H13

H13C6O

OC6H13

H13C6O

OC6H13

Scheme 8. Synthesis of cross-shaped π–conjugated meso-phenyl porphyrin derivatives.

8

N

HN

N

NH

I

I I

I

S+ N

HN

N

NH

S

S

S

S

H

H

H

H

nn

n n

N

N

N

N

S

S

S

S

H

H

H

H

nn

n n

Zn

n = 1, 2

H

Hn

n = 1, 2

n = 1, 2

9

S

H13C6O

OC6H13H

N

HN

N

NH

I

I I

I

+ H

n

N

HN

N

NH

SS

S

S

H

H

H

H

H13C6OOC6H13

OC6H13C6H13O

H13C6O

OC6H13

OC6H13

H13C6O

n

nn

n

n = 2, 4

N

HN

N

NH

SS

S

S

H

H

H

H

H13C6OOC6H13

OC6H13C6H13O

H13C6O

OC6H13

OC6H13

H13C6O

n

nn

n

n = 2, 4

n = 2, 4

N

HN

N

NH

I

I I

I

+ H N

HN

N

NH

H H

HH

H3

3

3

3

3

Scheme 9. Synthesis of cross-shaped π–conjugated meso-phenyl porphyrin derivatives.

10

N

HN

N

NH

SN

I

OC6H13

H13C6O

+N

HN

N

NH

S

N

S

N

C6H13O OC6H13

S

N

S

N

OC6H13H13C6O

H13C6O

OC6H13

OC6H13

H13C6O

Scheme 10. Synthesis of π–conjugated meso-phenyl porphyrin bearing peripheral pyridyl.

11

Doctoral Synthesis.

OH

OH

O

O

OH

OH

O

O

O

O

S

S Me

Me

O

O

O

O

O

O

Br

Br

O

O

N

N

N

N

HOCl

K2CO3

DMF, 110 oC

70% yield

MeSO2Cl, NEt3,DMAP/CH2Cl2

92.5% yield

LiBr

DMSO

50% yield

1)MeCN

2)KPF6

74% yield(R)-BEB

(R)-BINOL (R)-BE (R)-BES

(R)-BEBP

N N

2-PF6

1) DMF (110 oC)

2) KPF6

O

O

N

N

N

N(R)-BEBPB

Br

90% yield

4x PF-6

2) KPF6, 11% yield

1) MeCN, 110 oC

(R)-CBEBPB

O

O

N

N

N

N

4x PF6

Br

Br

Scheme 1. Synthesis of chiroptically switching molecules (R)-BEBPB and (R)-CBEBPB.

N NBr

N N

PPB

C3H7Br

O

O

Br

Br

(R)-BBEB

Br

Br

1) PPB, DMF (110 oC)

2) KPF6, 80.0 %

OO

N

N

N

N(R)-BBEBPP

PF64 x

Br

Br

O

O

Br

Br

Br2, CH2Cl2

(R)-BEB

12

Scheme 2. Synthesis of PPB and (R)-BBEBPP.

Br

Br

OO

OH

OH

HOCl

DMF, K2CO3

Br

Br

OHOH

OHOH CH2Cl2

-78 0C

Br2

(R)-DBB

Scheme 3. Synthesis of monomer (R)-DBB.

Pd(PPh3)4, K2CO3

THF/H2O (v/v, 1/1 )

MeSO2Cl, NEt3, DMAP

Br

Br

OOH

OOH

B B

C8H17 C8H17

O

O O

O+

95 oC

C8H17 C8H17

OOH

OHO

n

CH2Cl2

C8H17 C8H17

OOSO2Me

OMeO2SO

n

(R)-DBB

N N+Br

KI / DMF

80 oC

KI / DMF80 oC

C8H17 C8H17

OI

OI

n

P3

P1

P2

C8H17 C8H17

O

N+

O

N+

N+

N+

Br

Br

I

I

m

P4

Scheme 4. Synthetic route for optically active polymers P1, P2, P3 and P4.

13

1) HCl

CHCl3, Na2CO3/H2O

O

HO NaBrO3, NaHSO3

CH3COOC2H5CH2Br

O

HO SOCl2CH2Br

O

Cl

NH

OHN

CH3 O

OC(CH3)3

2) Na2CO3/H2O

NH2HOOC

HN

CH3 O

OC(CH3)3+

DCC, DMAP

THF

BBC

BBC NH

OHN

CH3

CH2Br

O

EM1

Br

CH3OH, 50oC

NH

OHN

CH3

CH2O

N N

2Br

EM2

EM3

N N

Scheme 5. Synthetic routes of monomers contained terminal acetylene.

NH

OHN

CH3

CH2Br

O THF

Rh(NBD)[B(C6H5)4]

N

N

CHC n

NH

OHN

CH3

CH2Br

O

CHC n

NH

OHN

CH3

H2C

O

N N

2 PF6-

Br

EM2 PEM2

1)

2)KPF 6

N

N

15

CHCl3

CHC n

NH

OHN

CH3

H2C

O

N N15

2Br

Br

PEM4

PEM5

Scheme 6. Synthetic routes of polyacetylenes.

14