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Supplementary Materials
Figure S1: Effect of cone voltage on positive mass spectra of [BuMeIm][Tf2N]: (a) 10V, (b)
20V, (c) 30V, (d) 40V, (e) 50V, (f) 60V.
Figure S2: Effect of cone voltage on negative mass spectra of [BuMeIm][Tf2N]: (a) 10V, (b)
20V, (c) 30V, (d) 40V, (e) 50V, (f) 60V.
Figure S3: (a) BuMeIm+ concentration before and after 2.0 MGy radiolysis determined by
HPLC and (b) Tf2N- concentrations before and after 2.0 MGy radiolysis determined by 19F
NMR in "dry" [BuMeIm][Tf2N], ½ w pre-eq [BuMeIm][Tf2N] and w pre-eq
[BuMeIm][Tf2N].
Figure S4: Evolution of X- (X- : Tf2N-, TfO-, PF6- and BF4-) concentration as a function of the
irradiation dose for [BuMeIm][Tf2N], [BuMeIm][TfO], [BuMeIm][PF6] and [BuMeIm][BF4].
Figure S5: Positive ESI-MS spectra of (a) [BuMeIm][Tf2N], (b) [BuMeIm][TfO], (c)
[BuMeIm][PF6] and (d) [BuMeIm][BF4] before radiolysis.
Figure S6: Positive ESI-MS spectra of (a) [BuMeIm][Tf2N], (b) [BuMeIm][TfO], (c)
[BuMeIm][PF6] and (d) [BuMeIm][BF4] after 2.0 MGy radiolysis.
Figure S7: MS/MS spectrum of ion at m/z 207.1.
Figure S8: MS/MS spectrum of ion at m/z 157.1.
Figure S9: MS/MS spectrum of ion at m/z 556.1.
Figure S10: Positive ESI-MS spectra of (a) "dry" [BuMeIm][Tf2N], (b) ½ w. pre-eq
[BuMeIm][Tf2N] and (c) w. pre-eq [BuMeIm][Tf2N] after 2.0 MGy radiolysis.
Figure S11: (a) UV spectra of [BuMeIm][Tf2N] before and after 2.0 MGy radiolysis (b)
Evolution of 290 nm light absorbance as a function of the irradiation dose for irradiated
[BuMeIm][Tf2N].
Figure S12: HPLC chromatograms of (a) [BuMeIm][Tf2N] after 2.0 MGy radiolysis at 210
nm and 290 nm light absorbance (b) [BuMeIm][TfO] after 2.0 MGy radiolysis at 210 nm and
290 nm light absorbance, (c) [BuMeIm][PF6] after 2.0 MGy radiolysis at 210 nm and 290 nm
light absorbance and (d) [BuMeIm][BF4] after 2.0 MGy radiolysis at 210 nm and 290 nm
light absorbance.
Figure S13: Total ion current gas chromatogram between 8.0 to 18.0 minutes of (a)
[BuMeIm][Tf2N], (b) [BuMeIm][TfO], (c) [BuMeIm][PF6], (d) [BuMeIm][BF4] after 50 kGy
radiolysis on Rt-MSieve/Rt-Q PLOT columns.
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139.1
%
100
(a)
558.1
139.9
0
139.1
%
100
558.1
140.1
(b)
0
139.1
%
100
558.1
140.1
(c)
0
%
100
139.1
140.1
(d)
325.9
139.1
140.1
325.8
501.3
325.9
447.2 501.3
0
%
100
(e)
0
558.1
139.1
100
%
558.1
140.1 211.2
(f)
0
100
200
300
400
500
558.1 621.3679.4
600
700
800
900
m/z
1000
Figure S1: Effect of cone voltage on positive mass spectra of [BuMeIm][Tf2N]: (a) 10V, (b) 20V, (c) 30V, (d) 40V, (e) 50V,
(f) 60V.
(a)
279.6
280.0
(b)
279.6
280.1
(c)
279.6
281.6
(d)
279.6
281.6
%
100
698.3
0
%
100
698.3
0
%
100
0
%
100
210.7
0
%
100
(e)
0
146.7
210.7
%
100
0
(f)
100
210.7
146.7
200
279.6
282.0
279.6
281.6
300
400
500
600
700
800
900
m/z
1000
Figure S2: Effect of cone voltage on negative mass spectra of [BuMeIm][Tf2N]: (a) 10V, (b) 20V, (c) 30V, (d) 40V, (e) 50V,
(f) 60V.
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Before Radiolysis
After 2,0 MGy Radiolysis
(a)
4,0
3,5
3,5
3,0
3,0
Before Radiolysis
After 2,0 MGy Radiolysis
(b)
[Tf2N] (mol.L )
-1
2,5
2,0
2,5
2,0
-
+
-1
[BuMeIm] (mol.L )
4,0
1,5
1,5
1,0
1,0
0,5
0,5
0,0
0,0
dry
1/2 w pre-eq
+
w pre-eq
dry
1/2 w-pre-eq
w-pre-eq
-
Figure S3 : (a) BuMeIm concentration before and after 2.0 MGy radiolysis determined by HPLC and (b) Tf2N
concentrations before and after 2.0 MGy radiolysis determined by 19F NMR in "dry" [BuMeIm][Tf2N], ½ w pre-eq
[BuMeIm][Tf2N] and w pre-eq [BuMeIm][Tf2N].
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Tf2N
TfO
PF6
BF4
6,0
5,0
X- (mol.L-1)
4,0
3,0
2,0
1,0
0,0
0
500
1000
1500
Dose (kGy)
2000
2500
Figure S4: Evolution of X- (X- : Tf2N-, TfO-, PF6- and BF4-) concentration as a function of the irradiation dose for
[BuMeIm][Tf2N], [BuMeIm][TfO], [BuMeIm][PF6] and [BuMeIm][BF4].
%
100
139.1
(a)
558.1
140.1
0
%
100
139.1
(b)
427.1
429.2
140.1
0
%
100
139.1
(c)
423.1
424.1
140.1
0
%
100
0
139.1
(d)
100
365.2
139.9
200
300
400
500
600
700
800
900
Figure S5: Positive ESI-MS spectra of (a) [BuMeIm][Tf2N], (b) [BuMeIm][TfO], (c) [BuMeIm][PF6] and (d)
[BuMeIm][BF4] before radiolysis.
m/z
1000
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BuMeImTf2N - irradie
139.1
137.1
100
207.1
100
%
(a)
%
100
BuMeImTf2N - irradie
157.1
119.0 125.1
63.1
0
80
100
239.1
182.1
83.1 103.0 119.0
60
201.1
0
m/z
120
150
175
200
225
286.1
250
275
m/z
300
%
558.1
BuMeImTf2N - irradie
558.1
100
139.4
140.1
%
559.1
560.1
207.1
561.1
0
100
200
300
400
500
600
BumimTfO irr - ESP+
139.1
556
700
557
558
800
900
m/z
559
m/z
1000
BumimTfO irr - ESP+
137.1
100
207.1
100
(b)
153.1
65.5 74.1
60
80
100
m/z
120
0
150
175
200
225
253.2
250
293.2
m/z
300
275
%
0
210.1
224.2
157.1
181.1
125.1
102.6 115.1
252.2
194.9
%
%
100
556.1
0
555
BumimTfO irr - ESP+
427.1
100
%
427.1
140.1
428.1
207.1
0
100
200
0
424
300
400
500
600
425
426
700
427
800
m/z
428
900
m/z
1000
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BuMeImPF6-2MGy
139.1
137.1
100
157.1
100
123.0
122.1
65.0 70.6 83.1 95.3
60
80
100
m/z
120
0
167.1 195.2 224.2 266.2
284.3
m/z
175 200 225 250 275 300
150
%
0
%
(c)
%
100
BuMeImPF6-2MGy
BuMeImPF6-2MGy
423.2
100
423.2
%
140.1
424.2
0
421.2
0
420
100
200
300
400
500
600
100
422
m/z
424
423
700
800
900
m/z
1000
BuMeImBF4-2MGy
BuMeImBF4-2MGy
139.1
421
137.1
100
157.1
100
(d)
118.0
120.0
56.7 69.5 76.8 92.5
60
80
116.0
100
136.0
158.1
m/z
120
0
150
175
252.2
277.2 293.2
m/z
225 250 275 300
210.1
200
%
0
%
%
224.2
182.2
BuMeImBF4-2MGy
365.2
100
365.2
157.1
0
%
140.1
364.2
364.2 366.2
363.2
0
362
100
200
300
400
500
600
363
364
700
365
800
365.5
m/z
366
900
Figure S6: Positive ESI-MS spectra of (a) [BuMeIm][Tf2N], (b) [BuMeIm][TfO], (c) [BuMeIm][PF6] and (d)
[BuMeIm][BF4] after 2.0 MGy radiolysis.
m/z
1000
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151.1
100
95
90
85
80
75
70
65
Relative Abundance
60
55
50
45
40
35
30
25
20
- C5H7F3
15
10
- C4H8
83.1
5
72.3
0
60
70
82.0
80
95.5
90
108.9
100
110
120.9 124.2 134.1 138.9 150.1
120
130
140
152.5
150
m /z
160
178.7
165.0
170
Figure S7: MS/MS spectrum of ion at m/z 207.1.
180
187.2
207.3
192.1 199.5
207.8
190
200
210
222.7
220
234.8 238.7 245.2
230
240
250
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137.1
100
95
90
85
80
75
70
65
Relative Abundance
60
55
50
45
- C4H7F
40
83.1
35
30
25
20
- C4H8
15
101.1
10
5
55.6
95.1
70.0 74.3
- HF
115.9 118.5
86.0
128.9
142.1
176.3
151.2 157.3
189.3
206.2
217.3
0
60
70
80
90
100
110
120
130
140
150
m /z
160
170
Figure S8: MS/MS spectrum of ion at m/z 157.1.
180
190
200
210
220
230
240
250
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091008-02 #1-44 RT: 0.04-1.99 AV: 44 NL: 4.09E3
T: + p ESI Full m s 2 [email protected] [ 150.00-1000.00]
275.2
100
95
90
85
80
75
70
65
193.2
Relative Abundance
60
55
50
-C4H6N2
45
40
35
30
25
20
219.2
15
-C4H8
10
5
261.3
163.1
-HTf2N
474.0
259.3
290.0
352.9
404.1 431.4
500.1
538.0 556.5
714.4
0
200
250
300
350
400
450
500
550
600
650
m /z
Figure S9: MS/MS spectrum of ion at m/z 556.1.
700
901.3
750
800
850
900
950
1000
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Tf2N
%
GL240209-10 95 (2.115)
x6 139.6
100
140.6
(a)
137.6
0
TOF MS ES+
9.26e3
207.6 242.7
181.6
558.3
556.3 559.3
420.3
334.4
%
GL240209-12 108 (2.405)
x6 139.6
100
140.6
(b)
TOF MS ES+
1.26e4
137.6 181.6 207.6
286.5 334.4
0
558.3
556.3 559.3
420.3
%
GL240209-14 5 (0.118)
x6 139.6
100
140.6
(c)
137.6 181.6
0
50
100
150
TOF MS ES+
1.26e4
207.6
200
286.5
250
326.3
300
363.6
350
558.3
556.3 559.4
420.3
400
450
500
550
m/z
600
Absorbance
Figure S10: Positive ESI-MS spectra of (a) "dry" [BuMeIm][Tf2N], (b) ½ w. pre-eq [BuMeIm][Tf2N] and (c) w. pre-eq [BuMeIm][Tf2N]
after 2.0 MGy radiolysis.
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
200
0.7
After Radiolysis
Before Radiolysis
250
300
350
nm
400
450
500
(b)
0.6
Absorbance
(a)
0.5
0.4
0.3
0.2
0.1
0.0
0
500000
1000000
Dose (Gy)
1500000
2000000
Figure S11: (a) UV spectra of [BuMeIm][Tf2N] before and after 2.0 MGy radiolysis (b) Evolution of 290 nm light
absorbance as a function of the irradiation dose for irradiated [BuMeIm][Tf2N].
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210 nm
290 nm
25000
Area (mAu)
Area (mAu)
(b)
20000
20000
15000
10000
z
5000
15000
z
10000
5000
0
0
8
13
210 nm
290 nm
25000
18
23
Time (min)
28
33
8
38
13
210 nm
290 nm
25000
(c)
18
23
Area (mAu)
z
15000
10000
28
33
38
33
38
Time (min)
(d)
z
20000
20000
Area (mAu)
210 nm
290 nm
25000
(a)
15000
10000
5000
5000
0
0
8
13
18
23
Time (min)
28
33
38
8
13
18
23
Time (min)
28
Figure S12: HPLC chromatograms of (a) [BuMeIm][Tf2N] after 2.0 MGy radiolysis at 210 nm and 290 nm light absorbance
(b) [BuMeIm][TfO] after 2.0 MGy radiolysis at 210 nm and 290 nm light absorbance, (c) [BuMeIm][PF6] after 2.0 MGy
radiolysis at 210 nm and 290 nm light absorbance and (d) [BuMeIm][BF4] after 2.0 MGy radiolysis at 210 nm and 290 nm
light absorbance.
Abundance
120000
100000
80000
60000
40000
Abundance
120000
100000
80000
60000
40000
Abundance
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120000
100000
80000
60000
40000
(a)
2.00
4.00
6.00
8.00
10.00
12.00
14.00
4.00
6.00
8.00
10.00
12.00
14.00
16.00
18.00
(c)
2.00
4.00
6.00
8.00
10.00
12.00
14.00
18.00
C4H7OH
C3H6
C2H6
C3H8
2.00
16.00
C4H8
C2H4
Abundance
18.00
(b)
2.00
120000
100000
80000
60000
40000
16.00
4.00
6.00
8.00
10.00
C4H10
C3H7F
12.00
14.00
(d)
C4H8
16.00
18.00
Time (min)
Figure S13: Total ion current gas chromatogram between 8.0 to 18.0 minutes of (a) [BuMeIm][Tf2N], (b) [BuMeIm][TfO],
(c) [BuMeIm][PF6], (d) [BuMeIm][BF4] after 50 kGy radiolysis on Rt-MSieve/Rt-Q PLOT columns.