dpv paper 2 suppdata - csiro publishing - excellence … · ! 6! supp figure 3. fluorescence decay...
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! 1!
Solvatochromism- in- diketopyrrolopyrrole- derivatives,- experimental- and-
computational-studies-
Jesse-Roth9Barton,1- Kenneth- P.- Ghiggino,1*- Rebecca- S.- Szabadai,1-Jonathan-M.-White,1*-
David-J.-D.-Wilson,2--
1)#School#of#Chemistry#and#BIO821#Institute,#The#University#of#Melbourne,#Victoria#3010#
2) Department of Chemistry, La Trobe Institute for Molecular Science, La Trobe University
Supplementary Material
Computational data 2
Photophysical data
SUPP Figure 1. Absorption-emission spectra 3
SUPP Figure 2. Absorption spectra in solvents of various polarities 4
SUPP Figure 3. Fluorescence decay data 6
1H and 13C data 7-16
! 2!
(1) Computational data
B3LYP/6-31G(d,p) calculated partial atomic charges of 2a-NMe as a function of solvent.a
S0 ground state S1 excited state thio DPP S O thio DPP S O Mulliken charges toluene 0.046 -0.092 0.270 -0.546 0.041 -0.083 0.263 -0.487 chloroform 0.050 -0.099 0.273 -0.553 0.046 -0.091 0.266 -0.494 THF 0.051 -0.102 0.275 -0.556 0.047 -0.095 0.268 -0.497 acetone 0.053 -0.106 0.277 -0.559 0.050 -0.100 0.270 -0.501 acetonitrile 0.054 -0.107 0.277 -0.560 0.051 -0.101 0.271 -0.502 water 0.054 -0.108 0.278 -0.561 0.051 -0.102 0.271 -0.503 NBO charges toluene 0.084 -0.167 0.457 -0.628 0.038 -0.075 0.429 -0.615 chloroform 0.087 -0.175 0.459 -0.635 0.044 -0.089 0.432 -0.622 THF 0.089 -0.178 0.461 -0.638 0.047 -0.095 0.433 -0.626 acetone 0.091 -0.182 0.463 -0.641 0.051 -0.102 0.435 -0.630 acetonitrile 0.091 -0.183 0.463 -0.642 0.052 -0.104 0.436 -0.631 water 0.092 -0.183 0.464 -0.643 0.053 -0.106 0.436 -0.632 a Atomic partial charges on S and O atoms, and sum of charges on the thiophene and DPP core groups.
! 3!
(2) Photophysical data
SUPP Figure 1. Absorption (blue) and emission (red) spectra of DPP derivatives 2c-2g in spectroscopic grade chloroform
0"
200"
400"
600"
800"
1000"
1200"
0"
0.05"
0.1"
0.15"
0.2"
0.25"
300" 400" 500" 600" 700" 800" 900" 1000"
Emission'Ab
sorban
ce''
Wavelength'(nm)'
2c'
0"
200"
400"
600"
800"
1000"
1200"
0"
0.05"
0.1"
0.15"
0.2"
0.25"
300" 400" 500" 600" 700" 800" 900"
Emission''A
bsorba
nce'
Wavelength'(nm)'
2d'
0"
200"
400"
600"
800"
1000"
1200"
0"
0.05"
0.1"
0.15"
0.2"
0.25"
300" 400" 500" 600" 700" 800" 900" 1000"
Emission''Ab
sorban
ce'
Wavelength'(nm)'
2e'
0"
200"
400"
600"
800"
1000"
1200"
0"
0.05"
0.1"
0.15"
0.2"
0.25"
300" 400" 500" 600" 700" 800" 900"
Emission''Absorban
ce'
Wavelength'(nm)'
2f'
0"
200"
400"
600"
800"
1000"
1200"
0"
0.05"
0.1"
0.15"
0.2"
0.25"
300" 400" 500" 600" 700" 800" 900" 1000"
Emssion'
Absorban
ce'
Wavelength'(nm)'
2g'
! 4!
SUPP Figure 2. Absorption spectra of compounds 2c-2g in solvents of varying polarity.
0"
0.2"
0.4"
0.6"
0.8"
1"
330" 430" 530" 630" 730"
Absorban
ce*(a
.u.)*
Wavelength*(nm)*
2c*Toluene"
THF"
Acetone"
Chloroform"
0"
0.2"
0.4"
0.6"
0.8"
1"
330" 430" 530" 630" 730"
Absorban
ce*(a
.u.)*
Wavelength*(nm)*
2d*Toluene"
THF"
Acetone"
Chloroform"
! 5!
0"
0.2"
0.4"
0.6"
0.8"
1"
330" 430" 530" 630" 730"
Absorban
ce*(a
.u.)*
Wavelength*(nm)*
2e*Toluene"
THF"
Acetone"
Chloroform"
0"
0.2"
0.4"
0.6"
0.8"
1"
330" 430" 530" 630" 730"
Absorban
ce*(a
.u.)*
Wavelength*(nm)*
2f*Toluene"
THF"
Acetone"
Chloroform"
0"
0.2"
0.4"
0.6"
0.8"
1"
330" 430" 530" 630" 730"
Absorban
ce*(a
.u.)*
Wavelength*(nm)*
2g*Toluene"
THF"
Acetone"
Chloroform"
! 6!
SUPP Figure 3. Fluorescence Decay Data and Results of Single Exponential Fitting for Compounds 2f and 2g.
-
Fitted lifetime!τf!;!Reduced chi-square fitting parameter!χ2 ;!Weighted residuals, fluorescence decay data, instrument response function and fitted curve. Solvent: chloroform; excitation wavelength: 400nm, emission wavelength: 650 nm.!!!Compound-2f-
τf!=!1.92!ns;!χ2 =1.05!!
!Residuals! !
!Fluorescence!decay!and!fitted!curve!Compound-2g-
τf!=!1.91!ns;!χ2 =1.08!!
ResidualsFluorescence!decay!and!fitted!curve!!!
020406080100120140160180200220
10.728
14.228
23.246
23.856
28.732
30.508
39.449
46.174
109.01
0
126.34
212
6.47
813
0.69
913
6.10
613
6.94
713
8.72
4
147.69
8
161.71
8
191.30
2
13C$Compound+2b+
7"
13.513.5
19.219.2
2.352.35
2.982.98
4.284.28
1.981.98
3.913.91
4.194.19
1.921.92
22
0011223344556677889910101111ppm-16.020
0.85
90.87
40.88
70.90
70.92
20.93
71.28
01.29
11.30
21.35
51.36
91.38
21.39
61.41
11.42
11.43
6
2.61
3
4.06
64.08
04.09
6
7.26
07.59
27.60
17.81
97.83
57.92
77.94
3
8.96
18.96
9
10.032
1H+$+Compound+2b+
8"
102030405060708090100110120130140150160ppm
10.711
14.240
23.261
23.829
28.675
30.481
30.491
31.083
39.415
46.227
103.80
4
108.90
011
1.41
4
121.33
112
3.67
212
5.49
912
5.60
812
8.99
012
9.67
9
136.67
913
8.07
713
9.73
5
150.14
6
155.11
8
161.77
4
13C+$+Compound+2c+
9"
12.812.8
17.317.3
1.971.97
4.164.16
1.921.92
3.43.4
2.072.07
2.072.07
3.863.86
22
0011223344556677889910101111ppm-16.020
0.07
20.87
90.89
30.90
70.91
70.93
20.94
71.27
51.28
61.29
61.30
81.32
11.37
51.38
51.39
91.41
21.42
71.43
71.93
31.94
21.94
71.95
31.96
6
4.04
64.07
64.09
24.10
94.13
9
7.04
67.04
87.24
07.24
27.25
87.26
07.27
27.31
27.31
57.32
97.34
37.50
67.50
87.52
37.52
47.57
77.58
6
8.99
89.00
7
1H+–+Compound+2c+
10"
0102030405060708090100110120130140150160170
10.768
14.251
23.276
23.871
28.705
30.502
39.460
46.213
108.80
511
2.07
1
118.12
612
5.55
812
6.16
012
6.42
812
9.27
712
9.53
312
9.91
013
0.24
113
4.05
513
4.45
613
5.05
713
7.13
013
9.88
714
0.96
714
8.39
8
161.78
5
13C+$+Compound+2d+
11"
11.611.6
1919
2.432.43
2.162.16
4.974.97
2.652.65
4.014.01
33
3.553.55
3.053.05
1.821.82
3.513.51
3.933.93
22
0011223344556677889910101111ppm-16.000
0.88
50.91
60.93
10.94
51.25
61.29
11.39
41.40
91.42
21.95
11.95
22.17
02.37
6
3.48
73.49
7
4.08
64.09
94.11
3
7.18
17.19
67.43
27.44
87.54
67.56
27.66
27.67
9
8.97
98.98
6
1H+–+Compound+2d+
12"
0102030405060708090100110120130140150160ppm
10.777
14.235
23.318
23.876
28.607
30.570
39.514
46.098
64.681
65.354
99.409
108.18
811
1.89
3
123.69
912
7.78
7
139.30
613
9.63
614
0.63
314
2.13
0
161.72
3
13C+$+Compound+2f+
13"
9.539.53
13.813.8
2.182.18
2.092.09
3.453.45
6.716.71
1.411.41
1.651.65
22
0011223344556677889910101111ppm-16.028
0.84
50.86
30.88
00.90
30.92
20.94
01.25
31.26
61.27
01.34
71.35
91.36
81.37
61.39
31.56
71.93
11.93
71.94
71.95
81.95
91.95
9
4.04
64.06
44.08
34.26
54.27
14.27
54.28
14.28
64.37
04.37
54.38
14.38
44.39
1
6.34
3
7.25
87.31
57.32
6
9.01
49.02
5
1H+–+Compound+2f+
14"
0102030405060708090100110120130140150160170
10.768
14.251
23.276
23.871
28.705
30.502
39.460
46.213
108.80
511
2.07
1
118.12
612
5.55
812
6.16
012
6.42
812
9.27
712
9.53
312
9.91
013
0.24
113
4.05
513
4.45
613
5.05
713
7.13
013
9.88
714
0.96
714
8.39
8
161.78
5
13C+$+Compound+2g++
15"
14.214.2
1818
2.422.42
4.294.29
10.510.5
7.647.64
3.853.85
22
0011223344556677889910101111ppm-16.028
0.86
70.86
90.87
40.88
50.90
20.92
10.94
00.95
81.28
41.28
51.28
61.28
71.29
41.30
51.37
01.37
71.37
91.38
41.40
11.42
01.42
01.93
51.93
51.93
61.94
21.94
31.94
41.94
51.94
51.95
01.95
14.08
44.09
44.10
4
7.25
87.40
57.42
27.44
07.45
97.51
77.54
07.55
17.67
97.68
17.68
57.69
97.70
37.74
37.76
47.93
97.96
08.99
89.00
8
1H+–+Compound+2g+
16"
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