Upload
others
View
3
Download
0
Embed Size (px)
Citation preview
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
S2.3 1H NMR spectrum of P2 .......................................................................................... 6
S2.4 1H NMR spectrum of P3 .......................................................................................... 7
S2.5 1H NMR spectrum of P4 .......................................................................................... 7
S2.6 1H NMR spectrum of P5 .......................................................................................... 8
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
2
S1. STM
S1.1 Fourier transformation
A
Size: 97.2 × 97.2 nm2
Iset=127pA, Vset=-860mV
Size: 119 × 119 nm2
Iset=127pA, Vset=-860mV
Fourier Analysis
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
3
B
Size: 96.4 × 96.4 nm2
Iset=189pA, Vset=-680mV
Size: 104 × 104 nm2
Iset=127pA, Vset=-860mV
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.
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
4
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
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
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
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
6
S2.2 1H NMR spectrum of P1
Figure S 4.
1H NMR (CS2/C2D2CL4) of P1.
S2.3 1H NMR spectrum of P2
Figure S 5.
1H NMR (CS2/C2D2CL4) of P2.
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
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
7
S2.4 1H NMR spectrum of P3
Figure S 6.
1H NMR (CS2/C2D2CL4) of P3.
S2.5 1H NMR spectrum of P4
Figure S 7.
1H NMR (CS2/C2D2CL4) of P4.
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
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
8
S2.6 1H NMR spectrum of P5
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
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
9
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.
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
10
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.
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
11
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.
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
12
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%.
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
13
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.
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013
14
S6. IR spectra of P1-P5
Figure S 18. IRspectrum P1.
Figure S 19. IRspectrum P2.
Figure S 20. IRspectrum P3.
Figure S 21. IRspectrum P3.
Figure S 22. IRspectrum P1.
Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013