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Electronic Supplementary Information (ESI)

Funnel shaped molecules containing benzo/pyrido[1,2,5]thiadiazole functionalities as peripheral acceptors for organic photovoltaic applications Mahalingavelar Paramasivama,b, Akhil Guptac,d, N. Jagadeesh Babue, K. Bhanuprakash*,b,f, Sheshanath V. Bhosale*,c and V. Jayathirtha Rao*,a,f

aCrop Protection Chemicals Division, CSIR- Indian Institute of Chemical Technology, Hyderabad 500007 India. E-mail: [email protected] and Physical Chemistry division, CSIR- Indian Institute of Chemical Technology, Hyderabad 500007 India; E-mail: [email protected] of Applied Sciences, RMIT University, GPO Box 2476, Melbourne VIC 3001 Australia; Email: [email protected] for Frontier Materials, Deakin University, Geelong Victoria 3216 AustraliaeCentre for X-ray Crystallography, CSIR-Indian Institute of Chemical Technology, Hyderabad, 500607, India.fCSIR-Network of Institutes for Solar Energy, New Delhi, India

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016

mailto:[email protected]

mailto:[email protected]

N1

23

4

5

6

7

8

9 10

11

1213

14

15

1617

18

19

N 20 N20'

32'

27'26'

21'

31' 30'

29'

28'

25'

24'23'

22'

212627

32

28

29

30 31

22

2324

25

3334

X3536

37

38

N39 S

41

N 40

X = C; DCTB

X = N; DCTP

N 1

3

2

410

11

1213

14

9

87

6

5

15

16

17

18

19

N 2021

2627

32 22

23

24252829

30

31

34'33'

38'37'

36'

X 35'

N39' S

41'

N 40'

34

X35

36

3738

33

N39

S41

N40

X = C; CTDB

X = N; CTDP

Bond Length DCTB DCTP

N1-C2 / N1-C3 1.421 / 1.421 1.423 / 1.422

N1-C4 / C2-C5 1.417 / 1.401 1.414 / 1.401

C5-C6 / C6-C7 1.389 / 1.398 1.389 / 1.398

C7-C8 / C8-C9 1.398 / 1.389 1.398 / 1.389

C9-C2 / C3-C10 1.401 / 1.401 1.401 / 1.401

C3-C14 / C10-C11 1.401 / 1.389 1.401 / 1.389

C11-C12 / C12-C13 1.398 / 1.398 1.398 / 1.398

C13-C14 / C4-C15 1.389 / 1.402 1.389 / 1.403

C4-C19 / C15-C16 1.403 / 1.388 1.404 / 1.387

C16-C17 / C17-C18 1.403 / 1.404 1.404 / 1.404

C18-C19 / C7-N20 1.387 / 1.419 1.386 / 1.418

C21-N20 / C32-N20 1.399 / 1.399 1.399 / 1.400

C21-C22 / C22-C23 1.396 / 1.389 1.396 / 1.389

C23-C24 / C24-C25 1.410 / 1.392 1.410 / 1.392

C25-C26 / C25-C26 1.399 / 1.447 1.399 / 1.447

C26-C27 / C28-C29 1.399 / 1.392 1.399 / 1.392

C29-C30 / C30-C31 1.410/ 1.389 1.410/ 1.389

C31-C32 / C17-C33 1.396 / 1.481 1.396 / 1.478

C33-C34 / C36-C37 1.443 / 1.448 1.448 / 1.448

C36-X35 / C34-X35 1.365 / 1.423 1.306 / 1.360

C37-C38/C38-C33 1.420 / 1.377 1.417 / 1.376

C36-N39 / C37-N40 1. 335 / 1.338 1. 335 / 1.335

N39-S41 / N40-S41 1.642/ 1.641 1.635/ 1.647

Bond Length CTDB CTDP

N1-C2 / N1-C3 1.422 / 1.419 1.426 / 1.416

N1-C4 / C2-C5 1.417 / 1.401 1.416 / 1.400

C5-C6 / C6-C7 1.389 / 1.398 1.389 / 1.399

C7-C8 / C8-C9 1.398 / 1.389 1.399 / 1.389

C9-C2 / C3-C10 1.401 / 1.402 1.400 / 1.402

C10-C11 / C11-C12 1.388 / 1.403 1.388 / 1.403

C12-C13 / C13-C14 1.403 / 1.388 1.404 / 1.387

C14-C3 / C4-C15 1.402 / 1.402 1.403 / 1.403

C15-C16 / C16-C17 1.387 / 1.404 1.387 / 1.404

C17-C18 / C18-C19 1.403 / 1.388 1.403 / 1.388

C7-N20 / C21-N20 1.419 / 1.399 1.417 / 1.400

C32-N20 / C21-C22 1.399 / 1.396 1.400 / 1.396

C22-C23 / C23-C24 1.389 / 1.410 1.389 / 1.410

C24-C25 / C25-C26 1.392 / 1.399 1.392 / 1.399

C26-C27 / C27-C28 1.447 / 1.399 1.447 / 1.399

C28-C29 / C29-C30 1.392/ 1.410 1.392/ 1.410

C30-C31 / C31-C32 1.389 / 1.396 1.389 / 1.396

C12-C33 / C33-C34 1.482 / 1.443 1.478/ 1.447

C34-X35 / X35-C36 1.365 / 1.423 1.306 / 1.360

C36-C37 /C37-C38 1.448 / 1.420 1.448 / 1.417

C36-N39 / C37-N40 1. 338 / 1.335 1. 335 / 1.335

N39-S41 / N40-S41 1.641/ 1.642 1.646/ 1.635

C38-C33 / C19-C4 1.377 / 1.402 1.377 / 1.402

Fig. S1. Geometrical Coordinates of target dyes.

Fig. S2. The ORTEP diagram of intermediate 6b with the atom-numbering scheme.

Displacement ellipsoids are drawn at the 30% probability level for non-hydrogen atoms and H

atoms are shown as small spheres of arbitrary radius.

Crystallographic data for DCTP: C48H40N8S2, M = 793.00, 0.43 x 0.21 x 0.12 mm3, triclinic,

space group P (No. 2), a = 12.4586(9), b = 14.8169(10), c = 15.6249(11) Å, α = 110.3700(10), 1̅

β = 99.7720(10), γ = 112.0440(10)°, V = 2351.8(3) Å3, Z = 2, Dc = 1.120 g/cm3, F000 = 832,

CCD area detector, MoKα radiation, λ = 0.71073 Å, T = 293(2)K, 2θmax = 50.0º, 8274 reflections

collected, 8274 unique (Rint = 0.0265), Final GooF = 0.998, R1 = 0.0712, wR2 = 0.1928, R

indices based on 6084 reflections with I >2σ(I) (refinement on F2), 529 parameters, 15 restraints

and μ = 0.153 mm-1.

Crystallographic data for Intermediate 6b: C23H14Br2N4S, M = 538.26, 0.32 x 0.19 x 0.12

mm3, monoclinic, space group P21/n (No. 14), a = 8.3446(12), b = 23.178(3), c = 10.9171(14) Å,

β = 94.496(3)°, V = 2105.0(5) Å3, Z = 4, Dc = 1.698 g/cm3, F000 = 1064, CCD area detector,

MoKα radiation, λ = 0.71073 Å, T = 293(2)K, 2θmax = 50.0º, 20022 reflections collected, 3696

unique (Rint = 0.0443), Final GooF = 1.024, R1 = 0.0504, wR2 = 0.1263, R indices based on

2718 reflections with I >2σ(I) (refinement on F2), 271 parameters and μ = 3.968 mm-1.

CCDC number of DCTP: 1038010

CCDC number of Intermediate 6b: 1038011

Table S1: Photophysical properties of the dyes

Dye λflua

(nm)

Stokes shift

(cm-1)

Φfc τd

(ns)

Kre

(109 s-1)

Knrf

(109 s-1)

KETg

(x 108 s-1)

DCTB 542 6000 0.13 6.61 0.019 0.13 1.51

DCTP 576 5627 0.18 7.29 0.024 0.11 1.37

CTDB 507 4667 0.11 5.11 0.022 0.17 1.96

CTDP 581 5883 0.16 7.03 0.023 0.12 1.42

aEmission spectra in toluene (solution concentration = 10-5 M) at ambient temperature. cFluorescence quantum yield measured in toluene; dExcited state lifetime in nanoseconds (ns); eRadiative decay constant (Kr= Φf/τ); fNon-radiative decay constant (Knr= (1-Φf)/τ)); gElectron

transfer rate constants (error limit of τ and KET ~10%).

Fig. S3. UV-Vis absorption spectra of the dyes in different solvents and thin film state.

Fig. S4. Normalized plots of simulated and experimental UV-Vis spectra of the dyes. The green

vertical bars correspond to the calculated singlet excited states in GaussSum 2.2.5.

Fig. S5. Photoluminescence spectra of the dyes in different solvents.

Table S2. Absorption maxima of the dyes in different solvents (units in nm).

Compound CHCl3 THF Hexane Toluene ACN DMF MeOHDCTB 414 408 403 409 402 410 406DCTP 449 433 436 435 428 436 430CTDB 416 411 406 410 405 414 408CTDP 444 434 436 433 428 437 429

Table S3. Emission maxima of the dyes in different solvents (units in nm).

Compound CHCl3 THF Hexane Toluene ACN DMF MeOHDCTB 616 602 560 616 -Q- -Q- -Q-DCTP 649 656 608 648 -Q- -Q- -Q-CTDB 573 574 531 573 -Q- -Q- -Q-CTDP 598 593 550 596 -Q- -Q- -Q-

Table S4. Stokes shift of the dyes in different solvents (units in cm-1).

Compound CHCl3 THF Hexane Toluene ACN DMF MeOHDCTB 7921 7899 6957 8216 - - -DCTP 6863 7851 6488 7556 - - -CTDB 6587 6909 5798 6937 - - -CTDP 5800 6178 4754 6316 - - -

Table S5. HOMO, LUMO energy values obtained from DFT studies

Dye HOMO(eV) LUMO (eV) Eg, HL (eV)

DCTB -5.25 -2.60 2.65

DCTP -5.32 -2.88 2.44

CTDB -5.35 -2.84 2.51

CTDP -5.47 -3.12 2.35

Table S6. Thermal data of the dyes

Dye Td (°C) Tg (°C) Tm (°C)

DCTB 434 148 313

DCTP 515 172 371

CTDB 389 189 316

CTDP 458 198 366

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0ppm

1.01

1.02

1.00

102030405060708090100110120130140150ppm

122.10

123.76

124.47

133.11

153.25

155.18

1H and 13C NMR spectra of molecule 1a

0.00.53.04.55.05.56.06.57.07.58.08.59.0ppm

1.02

1.00

1H and 13C NMR spectra of molecule 1b

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5ppm

15.95

2.30

1.00

0102030405060708090100110120130140150ppm

24.92

84.42

120.63

129.45

133.65

154.62

156.10


0.00.51.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0ppm

13.29

0.98

1.00

0102030405060708090100110120130140150160ppm

24.91

25.02

83.49

84.96

137.59

147.20

160.05

163.04


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5ppm

6.00

5.81

1H NMR spectrum of molecule 3

1H NMR spectrum of molecule 4

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0ppm

18.00

3.522.3510.30

1.94

7.07.17.27.37.47.5ppm

0102030405060708090100110120130140150ppm

32.09

34.77

109.23

116.13

116.29

123.36

123.57

124.93

125.66

125.89

127.70

132.60

133.33

142.93

145.54

1H and 13C NMR spectra of molecule 5

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0ppm

3.982.204.152.091.121.051.00

0102030405060708090100110120130140150ppm

116.28

117.73

121.54

123.98

126.04

128.52

129.87

132.60

133.98

141.59

146.09

147.31

154.13

155.50


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5ppm

3.912.083.832.06

0.99

1.00

0102030405060708090100110120130140150160170ppm

116.23

123.22

124.43

125.83

128.21

129.75

132.21

136.03

145.35

147.35

147.58

155.62

160.47


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5ppm

36.00

20.26

2.251.121.115.51

7.47.67.88.08.2ppm

0102030405060708090100110120130140150160ppm

32.14

34.84

109.33

116.38

117.77

121.58

123.41

123.70

124.34

125.56

127.86

128.67

139.38

142.92

145.90

147.92

154.21

155.62

1H and 13C NMR spectra of DCTB

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5ppm

36.00

2.1417.91

2.01

3.99

0.99

0.97

7.58.0ppm

0102030405060708090100110120130140150160ppm

32.13

34.83

109.29

116.38

123.45

123.70

123.98

124.90

125.91

127.92

128.29

128.85

129.10

130.17

133.94

136.70

139.34

143.00

145.60

147.96

148.71

156.23

161.02

1H and 13C NMR spectra of DCTP

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0ppm

18.00

8.384.254.092.042.053.95

7.407.447.487.52ppm

0102030405060708090100110120130140150160ppm

32.08

34.79

109.23

116.34

117.76

121.56

123.35

123.64

124.55

125.74

127.75

128.61

129.96

134.12

139.27

141.73

142.90

147.64

1H and 13C NMR spectra of CTDB

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5ppm

10.75

6.962.22

1.08

1.01

1.00

7.457.557.657.75ppm

0102030405060708090100110120130140150160170ppm

32.06

34.80

109.18

116.38

123.41

123.66

124.62

125.10

126.32

127.87

128.90

130.78

134.32

136.58

139.16

143.03

145.10

147.87

148.17

156.16

161.00

1H and 13C NMR spectra of molecule CTDP

GC-Mass spectrum of molecule 1a GC-Mass spectrum of molecule 1b

GC-Mass spectrum of molecule 2a GC-Mass spectrum of molecule 2b

GC-Mass spectrum of molecule 3 GC-Mass spectrum of molecule 4

EI-Mass spectrum of molecule 5

MALDI-TOF mass Spectrum of DCTB

IR Spectrum of DCTB

MALDI-TOF mass Spectrum of DCTP

IR Spectrum of DCTP

MALDI-TOF mass Spectrum of CTDB

IR Spectrum of CTDB

MALDI-TOF mass Spectrum of CTDP

IR Spectrum of CTDP

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