! 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"