SUPPORTING INFORMATION
Study of the controlled chain-growth polymerization of poly(3,6-phenanthrene)
Michiel Verswyvel, Charly Hoebers, Julien De Winter, Pascal Gerbaux and Guy Koeckelberghs
1.
1
H and 13C NMR spectrum of monomer 3 ............................................................................................. 2
2.
1
3.
1
4.
1
5.
MALDI-ToF spectra of 3,6-PPhs for the region m/z = 4300 to 4560 (Figure 4). .................................. 15
6.
MALDI-ToF spectra of 3,6-PPhs for the region m/z = 2590 to 4760 (Figure 5) ................................... 16
H NMR and mass spectra of the crude mixture of the ring walking experiment with Pd(PtBu3). ....... 4
H NMR spectra of GRIM of monomer 1 with iPrMgCl.LiCl at 25 °C ..................................................... 7
H NMR spectra of GRIM of monomer 1 with iPrMgCl.LiCl at 50 °C ................................................... 11
S1
5
4
-0.00
4.23
4.21
4.19
4.17
4.15
8.22
8.19
8.12
8.09
8.04
8.01
7.70
7.67
7.26
9.00
8.90
1.89
1.87
1.55
1.43
1.35
1.30
0.89
3
5.96
6
7.53
27.91
7
3.89
8
4.00
0.93
9
0.88
0.95
0.87
0.87
0.89
1. 1H and 13C NMR spectrum of monomer 3
2
0
1
ppm
Figure SI1 1H NMR spectrum of monomer 3.
S2
140
130
120
110
100
90
80
70
60
50
40
30
20
ppm
Figure SI2 13C NMR spectrum of monomer 3.
S3
14.12
31.85
30.47
30.45
29.49
29.32
26.25
26.23
24.93
22.68
84.03
77.45
77.02
76.60
73.71
73.63
143.97
143.30
132.69
132.12
130.35
129.98
129.75
128.19
126.75
125.55
124.08
121.44
120.26
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
6.09
7.5
39.85
8.0
6.83
8.5
1.77
2.00
9.0
0.86
0.90
0.84
1.77
0.95
1.78
0.91
0.78
0.85
8.89
8.88
8.65
8.64
8.34
8.31
8.11
8.08
7.89
7.89
7.86
7.86
7.80
7.80
7.78
7.72
7.72
7.69
7.69
7.55
7.53
7.53
7.50
7.41
7.26
4.28
4.25
4.23
4.20
4.17
4.15
1.88
1.87
1.86
1.85
1.85
1.84
1.83
1.65
1.59
1.54
1.41
1.37
1.36
1.35
1.34
1.31
1.30
1.27
1.24
1.23
1.21
1.19
0.92
0.90
0.89
0.88
-0.00
2. 1H NMR and mass spectra of the crude mixture of the ring walking experiment with Pd(PtBu3).
1.0
0.5
ppm
Figure SI3 1H NMR spectrum of the crude mixture of the ring walking experiment with Pd(PtBu3).
S4
Total spectrum (EI)
Figure SI4 Total mass spectrum of the crude mixture of the ring walking experiment with Pd(PtBu3).
S5
Zoom on m/z = 586 (EI) and simulation
a.i.
Figure SI5 Zoomed mass spectrum around the 586 peak of the crude mixture of the ring walking experiment with Pd(PtBu3).
m/z
Figure SI6 Simulated mass spectrum around the 586 peak of the start product 1 and the direacted phenanthrene 6.
S6
3. 1H NMR spectra of GRIM of monomer 1 with iPrMgCl.LiCl at 25 °C
The precursor monomer 1 was extensively dried over P2O5 and was repeatedly heated in a flask under reduced
pressure and finally set under argon atmosphere.
6.5
6.0
1.92
1.90
1.88
1.85
1.83
1.56
1.54
1.51
1.37
1.36
1.35
1.33
1.30
0.92
0.91
0.89
0.87
-0.00
4.19
4.17
4.15
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
ppm
3.12
7.0
2.57
8.50
7.5
2.07
8.0
0.91
0.12
8.5
0.07
0.86
0.06
0.06
0.92
9.0
2.00
8.22
8.22
8.11
8.10
8.08
8.07
7.72
7.71
7.70
7.69
7.68
7.67
7.66
7.64
7.64
7.63
7.62
7.61
7.60
7.59
7.26
After 30 min (quench in water)
Figure SI7 1H NMR spectrum of GRIM of monomer 1 with iPrMgCl.LiCl at 25 °C after 30 min reaction.
S7
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
3.23
7.5
3.66
8.75
8.0
2.63
8.5
2.00
9.0
0.87
0.21
0.09
0.79
0.10
0.10
0.89
1.90
1.88
1.87
1.85
1.83
1.58
1.56
1.54
1.52
1.51
1.40
1.37
1.36
1.35
1.33
1.30
0.92
0.91
0.89
0.87
-0.00
4.20
4.17
4.15
8.22
8.22
8.12
8.11
8.09
8.08
7.72
7.71
7.70
7.69
7.69
7.67
7.67
7.64
7.64
7.63
7.62
7.61
7.60
7.60
7.26
After 1 hour (quench in water)
1.0
0.5
ppm
Figure SI8 1H NMR spectrum of GRIM of monomer 1 with iPrMgCl.LiCl at 25 °C after 1 hour reaction.
S8
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
3.22
7.0
8.71
7.5
3.13
8.0
2.15
8.5
2.00
9.0
0.77
0.27
0.15
0.69
0.14
0.15
0.85
8.75
8.74
8.65
8.64
8.53
8.52
8.25
8.24
8.22
8.12
8.11
8.09
8.08
7.72
7.72
7.70
7.69
7.69
7.67
7.67
7.64
7.64
7.63
7.62
7.61
7.60
7.60
7.26
4.21
4.20
4.18
4.17
4.16
4.15
1.93
1.90
1.88
1.85
1.83
1.56
1.54
1.51
1.49
1.43
1.41
1.40
1.37
1.35
1.33
1.30
1.23
1.21
1.19
0.92
0.91
0.90
0.87
-0.00
After 2 hours (quench in water)
1.0
0.5
ppm
Figure SI9 1H NMR spectrum of GRIM of monomer 1 with iPrMgCl.LiCl at 25 °C after 2 hours reaction.
S9
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
3.33
7.5
5.67
8.79
8.0
2.06
8.5
2.00
9.0
0.70
0.39
0.15
0.58
0.17
0.16
0.77
1.90
1.88
1.85
1.56
1.51
1.43
1.41
1.37
1.35
1.33
1.30
0.92
0.91
0.90
0.87
-0.00
4.22
4.21
4.20
4.19
4.18
4.16
4.15
8.23
8.22
8.12
8.11
8.09
8.08
7.72
7.72
7.70
7.69
7.69
7.67
7.67
7.65
7.64
7.63
7.62
7.61
7.61
7.60
7.26
Overnight (quench in water)
1.0
0.5
ppm
Figure SI10 1H NMR spectrum of GRIM of monomer 1 with iPrMgCl.LiCl at 25 °C after overnight reaction.
S10
4. 1H NMR spectra of GRIM of monomer 1 with iPrMgCl.LiCl at 50 °C
The precursor monomer 1 was extensively dried over P2O5 and was repeatedly heated in a flask under reduced
pressure and finally set under argon atmosphere.
6.0
5.5
5.0
4.5
4.0
1.93
1.90
1.88
1.85
1.84
1.83
1.61
1.56
1.54
1.51
1.41
1.37
1.35
1.33
1.30
0.92
0.91
0.89
0.87
-0.00
3.5
3.0
2.5
2.0
1.5
1.0
0.5
ppm
3.28
6.5
4.44
8.76
7.0
2.33
7.5
2.00
8.0
0.70
0.38
8.5
0.18
0.59
0.16
0.17
0.81
9.0
4.21
4.19
4.18
4.17
4.16
4.15
8.22
8.22
8.12
8.11
8.09
8.08
7.72
7.72
7.70
7.69
7.69
7.67
7.67
7.64
7.64
7.63
7.62
7.61
7.60
7.60
7.26
After 30 min (quench in water)
Figure SI11 1H NMR spectrum of GRIM of monomer 1 with iPrMgCl.LiCl at 50 °C after 30 min reaction.
S11
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
3.38
7.0
3.78
8.87
7.5
2.63
8.0
2.00
8.5
0.67
0.40
9.0
0.22
0.78
0.19
0.48
0.18
8.75
8.74
8.65
8.64
8.55
8.53
8.52
8.25
8.24
8.22
8.22
8.12
8.11
8.09
8.08
7.72
7.72
7.70
7.69
7.69
7.67
7.67
7.64
7.64
7.63
7.62
7.61
7.60
7.60
7.26
4.21
4.20
4.19
4.17
4.16
4.15
1.90
1.88
1.88
1.86
1.85
1.84
1.83
1.58
1.54
1.51
1.43
1.41
1.39
1.37
1.35
1.33
1.30
0.92
0.91
0.90
0.87
-0.00
After 1 hour (quench in water)
1.0
0.5
ppm
Figure SI12 1H NMR spectrum of GRIM of monomer 1 with iPrMgCl.LiCl at 50 °C after 1 hour reaction.
S12
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
3.62
7.5
5.46
9.02
8.0
2.42
8.5
2.00
9.0
0.61
0.40
0.20
0.46
0.16
0.22
0.78
1.93
1.90
1.88
1.85
1.84
1.83
1.58
1.54
1.39
1.37
1.35
1.33
1.30
0.92
0.91
0.90
0.87
-0.00
4.22
4.21
4.20
4.19
4.17
4.16
4.15
8.22
8.12
8.11
8.10
8.09
8.08
7.72
7.72
7.70
7.69
7.69
7.67
7.67
7.65
7.64
7.63
7.62
7.61
7.61
7.60
7.26
After 2 hours (quench in water)
1.0
0.5
ppm
Figure SI13 1H NMR spectrum of GRIM of monomer 1 with iPrMgCl.LiCl at 50 °C after 2 hours reaction.
S13
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
4.65
7.0
10.95
7.5
6.75
8.0
2.39
8.5
2.00
9.0
0.66
0.38
0.18
0.45
0.16
0.18
0.81
1.0
0.5
-0.00
1.90
1.88
1.85
1.56
1.43
1.37
1.35
1.30
1.29
0.92
0.91
0.90
0.87
4.21
4.20
4.19
4.18
4.16
4.15
8.23
8.22
8.12
8.11
8.09
8.08
7.72
7.72
7.70
7.70
7.69
7.67
7.67
7.65
7.64
7.63
7.62
7.61
7.61
7.60
7.26
Overnight (quench in water)
ppm
Figure SI14 1H NMR spectrum of GRIM of monomer 1 with iPrMgCl.LiCl at 50 °C after overnight reaction.
S14
5. MALDI-ToF spectra of 3,6-PPhs for the region m/z = 4300 to 4560 (Figure 4).
(A) 30 min, (B) 50 min and (C) 150 min reaction time with 2.5 mol% Pd(PtBu3) initiator
Figure SI15 MALDI-ToF spectra of 3,6-PPhs for the region m/z = 4270 to 4620 for (A) 30 min, (B) 50 min and (C) 150 min reaction time with
2.5 mol% Pd(PtBu3) initiator.
S15
6. MALDI-ToF spectra of 3,6-PPhs for the region m/z = 2590 to 4760 (Figure 5)
(A) 50 min and (B) 150 min reaction time with 2.5 mol% Pd(PtBu3) initiator (c= 2.46  10-2 M in THF/H2O).
Figure SI16 MALDI-ToF spectra of 3,6-PPhs for the region m/z = 2590 to 4510 for (A) 50 min and (B) 150 min reaction time with 2.5 mol%
Pd(PtBu3) initiator (c= 2.46  10-2 M in THF/H2O).
S16
S17