Supporting Information
Synthesis of Polyarylacetylenes by -Ray Induced Polymerization of
Terminal Alkynes. Nanostructures of orto-Substituted Derivatives
Mauro Bassetti, Ilaria Fratoddi, Laura Lilla, Chiara Pasquini, Maria Vittoria Russo, Ornella
Ursini
Istituto CNR di Metodologie Chimiche, Sezione Meccanismi di Reazione, and
Dipartimento di Chimica, Sapienza Università di Roma, P.le A. Moro 5, 00185 Roma, Italy.
Dipartimento di Chimica and Centro delle Nanotecnologie per l’Ingegneria della Sapienza (CNIS), Sapienza
Università di Roma, P.le A. Moro 5, 00185 Roma, Italy.
Istituto CNR di Metodologie Chimiche, Area della Ricerca di Roma, 00016 Monterotondo Stazione (RM),
Italy.
List of Contents
-Irradiation of 4-RC6H4CCH (R = H, 1; CF3, 2; OMe, 3);
summary of polymerization data (Table S1)
page
S2
-Irradiation of 4-CF3C6H4CCH (2); summary of polymerization data (Table S2)
page
S3
-Irradiation of 2-RC6H4CCH (R = CF3, 4; OMe, 5) in THF;
summary of polymerization data (Table S3)
page
S3
Thermogravimetric analyses (TGA and DTG) of polymers P4-P6; Figure S1
page
S4
FT-IR spectrum of poly(o-CF3PA) (P4); Figure S2
page
S5
FT-IR spectrum of poly(o-OMePA) (P5); Figure S3
page
S6
FT-IR spectrum of poly(o-MePA) (P6); Figure S4
page
S7
19
page
S8
F NMR spectrum of poly(o-CF3PA) (P4) with deconvolution curves; Figure S5
1
H NMR and 13C NMR spectra of poly(o-OMePA) (P5); Figure S6
page
S9
1
H NMR spectrum of poly(o-MePA) (P6); Figure S7
page
S10
13
C NMR and 13C-DEPT NMR spectra of poly(o-MePA) (P6); Figure S8
page
S10
UV-Visible and photoluminescence spectra of polymers P4-P6; Figure S9
page
S11
SEM images of poly(o-CF3PA) (P4); Figures S10-S11
page
S12
S1
Table S1. Polymerization Data of the Materials Formed in Solution upon -Ray Irradiation (100
kGy) of Alkynes (4-RC6H4CCH) in Different Solvents.a,b
Đd
hexane
Mn,c
g mol–1
1220
Mw,c
g mol–1
1530
1.25
78
1 (H)
dioxane
640
900
1.41
90
3
1 (H)
ethylacetate
350
460
1.32
74
4
1 (H)
methanol
5
2 (CF3)
hexane
6
2 (CF3)
dioxane
880
3300
1070
2250
500
1250
3365
1190
2280
640
1.43
1.02
1.10
1.02
1.28
78
21
57
31
79
7
2 (CF3)
ethylacetate
710
880
1.23
78
8
2 (CF3)
methanol
9
3 (OMe)
hexane
1320
2720
830
1450
2770
1080
1.11
1.02
1.30
49
37
92
10
3 (OMe)
dioxane
830
1060
1.28
90
11
3 (OMe)
ethylacetate
920
1200
1.30
91
12
3 (OMe)
methanol
1130
1420
1.26
84
entry
alkyne (R)
solvent
1
1 (H)
2
(%)e
a) Phenylacetylene (1); 1-ethynyl-4-(trifluoromethyl)benzene (2); 1-ethynyl-4-methoxybenzene
(3). b) alkyne(50 L)/solvent = 1:1, v:v. c) determined by GPC in chloroform and based on
polystyrene standards. d) Molecular weight dispersity, Mw/Mn. e) Area% of the GPC band.
S2
Table S2. Polymerization Data of the Materials Formed in Solution upon -Ray Irradiation of 4CF3C6H4CCH (2, 100 L) under Different Irradiation Doses and Dilutions.
Mw,
g mol–1
1360
Đ
(%)b
50
Mn,
g mol–1
1150
1.18
80
neat
200
840
990
1.18
84
hexane
1:1
50
1120
1320
1.18
86
4
hexane
1:1
100
1140
1340
1.17
88
5
hexane
1:1
200
500
590
1.19
71
6
hexanec
1:5
200
840
1040
1.24
100
7
methanol
1:1
50
8
methanol
1:1
100
9
methanol
1:1
200
10
methanol
1:5
50
11
methanol
1:5
100
12
methanol
1:5
200
460
1070
1180
2320
480
990
830
1670
940
1920
1303
530
1100
1280
2360
520
1000
900
1720
1020
1960
1470
1.14
1.02
1.08
1.02
1.10
1.02
1.08
1.02
1.08
1.02
1.13
59
29
53
37
53
38
46
47
48
47
100
entry
solvent
dilutiona
1
neat
neat
2
neat
3
kGy
a) 2:solvent (v:v). b) Relative area% of the GPC band. c) A red precipitate separated from the
solution.
Table S3. Polymerization Data of the Materials Formed in Solution upon -Ray Irradiation of 2CF3C6H4CCH (4) and 2-MeOC6H4CCH (5) in Tetrahydrofuran at rt.a
dilutionb
kGy
Mn
Mw
Đ
1
alkyne
(2-R)
4 (CF3)
1:10
200
6250
7160
1.14
solution
colour
dark red
2c
4 (CF3)
1:10
400
2880
3250
1.12
light red
3
4 (CF3)
1:10
400
4930
5710
1.16
dark red
4
5 (OMe)
1:10
200
4300
4830
1.12
k5
5 (OMe)
1:10
400
3270
3890
1.19
orange
(fluorescent)
orange
entry
a) Reaction conditions: 400 l of alkyne in 4 mL of THF. b) alkyne:THF (v:v). c) In air.
S3
Figure S1. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA, top) of
poly(o-RPA) (R = CF3, P4; OMe, P5; Me, P6), performed under nitrogen.
S4
cf3 2etinil 1a10 me
1173.15
1604.97
1577.07
1490.81
1448.32
2500
2000
Wavenumber cm-1
1500
1315.08
1264.35
3000
Page 1/1
1053.26
1035.46
957.29
3071.66
3500
cf3 2etinil 1a10 meoh 400 kgy sample 9 film08/07/2011
da chcl3
1000
766.79
4000
C:\Documents and Settings\utente\Desktop\cf3 2etinil 1a10 meoh 400 kgy sample 9 film da chcl3.0
500
652.03
599.95
60
70
Transmittance [%]
80
90
100
110
Figure S2. FT-IR spectrum of poly(o-CF3PA) (P4) as thin film cast on ZSM-5 window from
chloroform solution. Sample obtained under the following irradiation conditions: 1-ethynyl-2trifluoromethyl)benzene (4) in MeOH (1:10, v:v), 400 kGy.
S5
1290.99
1246.99
1180.64
1161.61
1117.24
1029.40
1731.27
1682.29
1597.92
1580.61
1490.29
1462.86
1434.22
2500
2000
Wavenumber cm-1
1500
1000
750.79
3000
2832.34
3000.96
2939.16
3500
Page 1/1
2 OMe3 1a10 MeOH 40
667.68
4000
C:\Documents and Settings\utente\Documenti\articoli\radiolisi raggi gamma 2010\ir mauro polimeri da irragiamento\2 OMe3 1a10 MeOH 400KGy sample
08/07/2011
D.0
500
580.32
70
Transmittance [%]
80
90
100
110
Figure S3. FT-IR spectrum of poly(o-OMePA) (P5, neat) as thin film cast on ZSM-5 window from
chloroform solution. Sample obtained under the following irradiation conditions: 1-ethynyl-2methoxybenzene (5) in MeOH (1:10, v:v), 400 kGy.
S6
Page 1/1
1035.51
1577.75
1560.36
1542.39
1508.45
1488.44
1458.10
1377.11
1260.95
1219.12
2500
2000
1500
Wavenumber cm-1
1000
770.82
730.00
668.96
2922.72
3000
C:\Documents and Settings\utente\Documenti\articoli\radiolisi raggi gamma 2010\ir mauro polimeri da irragiamento\oMe 1a10 MeOH 200KGy sample 08/07/2011
F.0
oMe 1a10 MeOH 200KGy samp
500
454.25
419.22
3057.95
3016.54
100
102
104
Transmittance [%]
106 108 110
112
114
Figure S4. FT-IR spectrum of poly(o-MePA) (P6, neat) as thin film cast from chloroform solution
on a ZSM-5 window. Sample obtained under the following irradiation conditions: 2-ethynyltoluene
(6) in MeOH (1:10, v:v), 200 kGy.
S7
Figure S5.
19
F NMR spectrum of poly(o-CF3PA) (P4) and deconvoluted signals: -54.5 ppm (blue
trace, 4%), -57.0 ppm (green trace, 52%), -57.7 ppm (violet trace, 44%).
S8
Figure S6. 1H NMR spectrum (300 MHz, top trace) and 13C NMR spectrum (75.5 MHz, bottom
trace) of poly(o-OMePA) (P5) in CDCl3 solutions.
S9
Figure S7. 1H NMR spectrum of poly(o-MePA) (P6) in CDCl3 ((300 MHz).
Figure S8. 13C NMR (top trace) and 13C DEPT NMR (bottom trace) spectra of poly(o-MePA) (P6)
in CDCl3 (75.5 MHz).
S10
FIGURA Spettri di assorbimento in cloroformio non normalizzata
P4 MCU1 polimero oCF3 :MeOH 1:5, 200 KGy
P5 MCU11D polimero oOMe :MeOH
1:10, 400 KGy
Spettri di emissione in cloroformio
P6 MCU12 polimero oMe :MeOH 1:10,
400 KGy
P4 MCU1 polimero oCF :MeOH 1:5, 200 KGy
3
P5 MCU11D polimero oOMe :MeOH 1:10, 400 KGy
P6 MCU12 polimero oMe :MeOH 1:10, 400 KGy
1,0
1,0
0,8
Normalized I (a.u.)
P5
P6
P4
0,6
0,8
0,6
0,4
0,2
A
0,0
400
450
500
550
600
650
700
 (nm)
0,4
0,2
0,0
270
300
330
360
390
420
450
480
510
540
570
600
 (nm)
Figure S9. UV-visible spectra of poly(o-RPA) (R = CF3, P4; OMe, P5; Me, P6) in CHCl3. The
normalized photoluminescence spectra are shown in the inset.
S11
Figure S10. SEM image of poly(o-CF3PA) (P4) obtained by drop casting of a toluene solution
(1 mg/mL) at room temperature.
Figure S11. SEM image of poly(o-CF3PA) (P4) obtained from the osmosis based method in
DMSO/H2O. Scale bars are 1 m.
S12