influence of the regioregularity on the chiral ... · influence of the regioregularity on the...

1

Supporting Information

Influence of the regioregularity on the chiral

supramolecular organization of poly(3-

alkylsulfanylthiophene)s.

Helmuth Peeters, Pauline Couturon, Steven Vandeleene, David Moerman, Philippe Leclère,

Roberto Lazzaroni, Inge De Cat, Steven De Feyter and Guy Koeckelberghs

Table of contents

S1. STM ................................................................................................................................. 2

S1.1 Fourier transformation ............................................................................................. 2 S1.2 Histograms ............................................................................................................... 4

S2. 1H NMR spectra .............................................................................................................. 5

S2.1 1H NMR spectrum of quench 2a’ and (2a + 2b) with D2O ...................................... 5

S2.2 1H NMR spectrum of P1 .......................................................................................... 6





S3. UV-vis spectra ................................................................................................................. 9 S3.1 P1 and P2 in CHCl3/CS2 .......................................................................................... 9

S4. Solvatochromism experiment of P1-5 ........................................................................... 10 S4.1 Deconvolution of UV-vis spectra of P1-P5 ........................................................... 12

S5. Emission spectroscopy of P1-P5 ................................................................................... 13 S5.1 Emission spectroscopy of P1-P5 in CHCl3 ............................................................ 13 S5.2 Emission spectroscopy of P1 in CHCl3/CS2 (8/2) ................................................. 13

S6. IR spectra of P1-P5 ....................................................................................................... 14

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013

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S1. STM

S1.1 Fourier transformation

A

Size: 97.2 × 97.2 nm2

Iset=127pA, Vset=-860mV

Size: 119 × 119 nm2


Fourier Analysis


3

B

Size: 96.4 × 96.4 nm2


Size: 104 × 104 nm2


Fourier Analysis

Figure S 1. STM images and the Fourier transformation of the regioregular P3AST (A) and

regio-irregular P3AST (B) at the 1,2,4-TCB/graphite interface. The polymers used are the

same as described in Macromolecules, 2008, 41, 5123-5131.


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S1.2 Histograms

A

B

Figure S 2. Histograms showing the distribution of the lengths and DP of self-assembled of

the regioregular P3AST (A) and the regio-irregular P3AST (B) chains at the 1,2,4-

TCB/graphite interface.

0

10

20

30

40

Nu

mb

er

of

chai

ns

Chain length (nm)

05

10152025303540

Nu

mb

er

of

chai

ns

DP

0

5

10

15

20

25

Aan

tnu

mb

er

of

chai

nss

Chain length (nm)

0

5

10

15

20

25

nu

mb

er

of

chai

ns

DP


5

S2. 1H NMR spectra

S2.1 1H NMR spectrum of quench 2a’ and (2a + 2b) with D2O

Figure S 3.

1H NMR (CDCl3) of the aromatic region of the quench of 2a’ and (2a + 2b) with

D2O.

2a’

2a + 2b


6

S2.2 1H NMR spectrum of P1

Figure S 4.

1H NMR (CS2/C2D2CL4) of P1.


Figure S 5.


1.01.52.02.53.03.54.04.55.05.56.06.57.07.5 ppm

1.01.52.02.53.03.54.04.55.05.56.06.57.07.5 ppm


7


Figure S 6.



Figure S 7.


1.01.52.02.53.03.54.04.55.05.56.06.57.07.5 ppm

1.01.52.02.53.03.54.04.55.05.56.06.57.07.5 ppm


8


Figure S 8.

1H NMR (CS2/C2D2Cl4) of P5.

1.01.52.02.53.03.54.04.55.05.56.06.57.07.5 ppm


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S3. UV-vis spectra

S3.1 P1 and P2 in CHCl3/CS2

400 500 600 7000

3000

6000

9000

(M

-1.c

m-1)

Wavelength (nm)

P1 CHCl3/CS

2

P1 CHCl3

A

400 500 600 7000

3000

6000

9000

P2 CHCl3/CS

2

P2 CHCl3

(M

-1.c

m-1)

Wavelength (nm)

B

Figure S 9. Complete dissolution of P1(A) and P2(B) in CHCl3/CS2 vs P1 in CHCl3.


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S4. Solvatochromism experiment of P1-5

S4.1 Solvatochromism

300 400 500 600 7000

3000

6000

9000

12000 100/0

90/10

85/15

80/20

78/22

75/25

70/30

65/35

60/40

50/50

40/60

(M

-1.c

m-1)

Wavelength (nm)

A

300 400 500 600 700

-60

-40

-20

0

20

100/0

90/10

85/15

80/20

78/22

75/25

70/30

65/35

60/40

50/50

40/60

(M-1.c

m-1)

Wavelength (nm)

B

Figure S 10. Solvatochromism experiment of P1 in CHCl3/MeOH mixtures: A) UV-vis

spectra and B) CD spectra.

300 400 500 600 7000

3000

6000

9000

12000

(M

-1.c

m-1)

Wavelength (nm)

100/0

95/5

90/10

85/15

80/20

75/25

73/27

70/30

60/40

50/50

C

300 400 500 600 700

-100

-80

-60

-40

-20

0

20

100/0

95/5

90/10

85/15

80/20

75/25

73/27

70/30

60/40

50/50

(M-1.c

m-1)

Wavelength (nm)

D

Figure S 11. Solvatochromism experiment of P2 in CHCl3/MeOH mixtures: C) UV-vis

spectra and D) CD spectra.

300 400 500 600 7000

3000

6000

9000

12000

(M

-1.c

m-1)

Wavelength (nm)

100/0

95/5

90/10

85/15

80/20

75/25

72/28

70/30

60/40

50/50

E

300 400 500 600 700

-60

-40

-20

0

20

100/0

95/5

90/10

85/15

80/20

75/25

72/28

70/30

60/40

50/50

(M-1.c

m-1)

Wavelength (nm)

F

Figure S 12. Solvatochromism experiment of P3 in CHCl3/MeOH mixtures: E) UV-vis

spectra and F) CD spectra.


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300 400 500 600 7000

3000

6000

9000

(M

-1.c

m-1)

Wavelength (nm)

100/0

90/10

80/20

70/30

65/35

60/40

55/45

50/50

45/55

G

300 400 500 600 700

-30

-20

-10

0

10

100/0

90/10

80/20

70/30

65/35

60/40

55/45

50/50

45/55

(M-1.c

m-1)

Wavelength (nm)

H

Figure S 13. Solvatochromism experiment of P4 in CHCl3/MeOH mixtures: G) UV-vis

spectra and H) CD spectra.

300 400 500 600 7000

3000

6000

9000

(M

-1.c

m-1)

Wavelength (nm)

100/0

90/10

80/20

70/30

65/35

60/40

50/40

45/55

40/60

I

300 400 500 600 700

-30

-20

-10

0

10

20

100/0

90/10

80/20

70/30

65/35

60/40

50/40

45/55

40/60

(M-1.c

m-1)

Wavelength (nm)

J

Figure S 14. Solvatochromism experiment of P5 in CHCl3/MeOH mixtures: I) UV-vis spectra

and J) CD spectra.


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S4.2 Deconvolution of UV-vis spectra of P1-P5

300 400 500 600 7000,0

0,2

0,4

0,6

0,8

1,0

Absorb

ance (

a.u

.)

Wavelength (nm)

P1 measured

band 1

band 2

band 3

Band 4

Band 5

A

300 400 500 600 7000,0

0,2

0,4

0,6

0,8

1,0

Absorb

ance (

a.u

.)

Wavelength (nm)

P2 measured

band 1

band 2

band 3

Band 4

Band 5

B

300 400 500 600 7000,0

0,2

0,4

0,6

0,8

1,0

Absorb

ance (

a.u

.)

Wavelength (nm)

P3 measured

band 1

band 2

band 3

Band 4

Band 5

C

300 400 500 600 7000,0

0,2

0,4

0,6

0,8

1,0

Absorb

ance (

a.u

.)

Wavelength (nm)

P4 measured

band 1

band 2

band 3

Band 4

Band 5

D

300 400 500 600 7000,0

0,2

0,4

0,6

0,8

1,0

Absorb

ance (

a.u

.)

Wavelength (nm)

P5 measured

band 1

band 2

band 3

Band 4

Band 5

E

Figure S 15. Deconvolution of UV-vis spectra of P1-P5 in poor solvent mixtures. The band

near 610 nm, which probes π interactions, was filled and the relative integration was

calculated. A) P1 CHCl3/MeOH (50/50); 15.3%, B) P2 CHCl3/MeOH (60/40); 17.8%, C) P3

CHCl3/MeOH (60/40); 13.5%, D) P4 CHCl3/MeOH (55/45); 9.2%, E) P5 CHCl3/MeOH

(45/55); 8.9%.


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S5. Emission spectroscopy of P1-P5

S5.1 Emission spectroscopy of P1-P5 in CHCl3

500 550 600 650 700 7500,0

2,0x105

4,0x105

6,0x105

8,0x105

P1

P2

P3

P4

P5

Em

issio

n (

a.u

.)

Wavelength (nm) Figure S 16. Emission spectra of P1-P5 in CHCl3 excited at 500 nm.

S5.2 Emission spectroscopy of P1 in CHCl3/CS2 (8/2)

500 550 600 650 700 7500,0

2,0x105

4,0x105

6,0x105

Em

issio

n (

a.u

.)

Wavelength (nm)

P1

P2

P3

Figure S 17: Emission spectra of P1-P3 in CHCl3/CS2 (8/2) excited at 500 nm.


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S6. IR spectra of P1-P5

Figure S 18. IRspectrum P1.






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