Universidad de Castilla-La Mancha. Institute of Nanoscience, … · 2017-02-27 · New...

26
New Acceptor-π-Porphyrin-π-Acceptor Systems for Solution-Processed Small Molecule Organic Solar Cells Susana Arrechea, a Agustín Molina-Ontoria, b Ana Aljarilla, a Pilar de la Cruz, a Fernando Langa a,* and Luis Echegoyen b,* a Universidad de Castilla-La Mancha. Institute of Nanoscience, Nanotechnology and Molecular Materials (INAMOL), Campus de la Fábrica de Armas, Toledo, Spain; Fax: 34 9252 68840; Tel: 34 9252 68843; E-mail: [email protected] b Department of Chemistry, University of Texas at El Paso, El Paso, TX 79968, USA.; Tel: 915-747-7573; E-mail: [email protected] Table of contents 1. Experimental details S2 2. 1 H-NMR, 13 C-NMR, FT-IR and MALDI-TOF o MS spectra S5 3. Thermogravimetric analysis S21 4. UV-Visible and emission spectroscopies S22 5. Square Wave plots S24 6. EQE and IV characteristic for 1a:PC71BM (1:2) S26

Transcript of Universidad de Castilla-La Mancha. Institute of Nanoscience, … · 2017-02-27 · New...

Page 1: Universidad de Castilla-La Mancha. Institute of Nanoscience, … · 2017-02-27 · New Acceptor-π-Porphyrin-π-Acceptor Systems for Solution-Processed Small Molecule Organic Solar

New Acceptor-π-Porphyrin-π-Acceptor Systems for Solution-Processed Small

Molecule Organic Solar Cells

Susana Arrechea,a Agustín Molina-Ontoria,b Ana Aljarilla,a Pilar de la Cruz,a

Fernando Langaa,* and Luis Echegoyenb,*

a Universidad de Castilla-La Mancha. Institute of Nanoscience, Nanotechnology and

Molecular Materials (INAMOL), Campus de la Fábrica de Armas, Toledo, Spain; Fax:

34 9252 68840; Tel: 34 9252 68843; E-mail: [email protected]

bDepartment of Chemistry, University of Texas at El Paso, El Paso, TX 79968, USA.;

Tel: 915-747-7573; E-mail: [email protected]

Table of contents

1. Experimental details S2

2. 1H-NMR, 13C-NMR, FT-IR and MALDI-TOF o MS spectra S5

3. Thermogravimetric analysis S21

4. UV-Visible and emission spectroscopies S22

5. Square Wave plots S24

6. EQE and IV characteristic for 1a:PC71BM (1:2) S26

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1. Experimental details

Synthetic procedures were carried out under inert argon atmosphere, in dry

solvent unless otherwise noted. All reagents and solvents were reagent grade and

were used without further purification. Chromatographic purifications were

performed using silica gel 60 SDS (particle size 0.040-0.063 mm). Analytical thin-

layer chromatography was performed using Merck TLC silica gel 60 F254. 1H-NMR

spectra were obtained on Bruker TopSpin AV-400 (400 MHz) spectrometer.

Chemical shifts are reported in parts per million (ppm) relative to the solvent

residual peak (CDCl3, 7.27 ppm). 13C-NMR chemical shifts () are reported relative

to the solvent residual peak (CDCl3, 77.0 ppm). UV-Vis measurements were carried

out on a Shimadzu UV 3600 spectrophotometer. For extinction coefficient

determination, solutions of different concentration were prepared in CH2Cl2 (HPLC

grade) with absorption between 0.1-1 of absorbance using a 1 cm UV cuvette. The

emission measurements were carried out on Cary Eclipse fluorescence

spectrophotometer. Mass spectra (MALDI-TOF) were recorded on a VOYAGER

DETM STR mass spectrometer using dithranol as matrix. Melting points are

uncorrected.

The molecular geometries and frontier molecular orbitals of these new dyes have

been optimized by density functional theory (DFT) calculations at the B3LYP/6-31G*

level.1

1 Gaussian 03, Revision D.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G.

E.; Robb, M. A.; Cheeseman, J. R.; Montgomery Jr., J. A.; Vreven, T.; Kudin, K. N.;

Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi,

M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.;

Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.;

Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.;

Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.;

Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.;

Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain,

M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.;

Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu,

G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-

Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.;

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Cyclic voltammetry was performed in ODCB-acetonitrile (4:1) solutions.

Tetrabutylammonium perchlorate (0.1 M as supporting electrolyte) were

purchased from Acros and used without purification. Solutions were deoxygenated

by argon bubbling prior to each experiment which was run under argon

atmosphere. Experiments were done in a one-compartment cell equipped with a

platinum working microelectrode ( = 2 mm) and a platinum wire counter

electrode. An Ag/AgNO3 (0.01 M in CH3CN) electrode was used as reference and

checked against the ferrocene/ferrocenium couple (Fc/Fc+) before and after each

experiment.

The thermal stability was evaluated by TGA on a Mettler Toledo TGA/DSC Starte

System under nitrogen, with a heating rate of 10 ºC/min. Heating of crystalline

samples leads to melting of the solids, but no recrystallization was observed.

SM BHJ device preparation

PC61BM and PC71BM were purchased from American Dye Source and used as

recieved.

The ITO-coated glasses (Delta technologies, 5-15 Ω) were pre-cleaned stepwise by

ultracentrifugation 15 minutes in detergent, deionized water, methanol, acetone

and iso-propanol and then by a 30 minutes UV-ozone treatment. A thin layer of

PEDOT:PSS (Clevios P VP AI 4083, 5000 rpm, 30 seconds, 30 nm) was spin-

coated onto the ITO and baked at 150 ºC for 15 minutes in air. Subsequently, the

active layer (1a-b:PC61BM, 30 mg/mL) with varying weight ratios (1:4, 1:2 and

1:1) was spin-coated at 1500 rpm from chlorobenzene solutions. 1a or 1b, 1a-

b:PC71BM (1:2, 30 mg/mL) was spin-coated at 1500 rpm. Then the devices were

transferred to a N2 filled glove box (<0.1 ppm O2 and < 0.1 ppm H2O) for further

processing. The photoactive layer was annealed at 80 ºC for 10 minutes followed

by thermal evaporation of 20 nm of calcium and 80 nm of aluminum (1 x 10-6

mbar) with a shadow mask of 0.4 cm2. The photovoltaic properties were measured

under 1 sun, AM1.5G (air mass 1.5 global) spectrum from a solar simulator (Photo

Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian, Inc.,

Wallingford CT, 2004.

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Emission Tech CT100) at 100 mW/cm2). The Jsc–Voc characteristics were

recorded with a Keithley 2420 source unit.

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2. 1H NMR, 13C NMR, FT-IR and MALDI-TOF MS spectra

Figure S1. 1H NMR spectrum (400 MHz, CDCl3) of 3a.

Figure S2. 13C NMR spectrum (100 MHz, CDCl3) of 3a.

2345678910111213 ppm

1.342100

1.349200

1.358300

1.366100

1.565300

1.583200

2.194800

2.531400

2.553000

2.570800

2.899000

2.919100

2.938800

9.904600

6.7

6.8

5.3

2.5

2.0

2.1

1.0

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Figure S3. 1H NMR spectrum (400 MHz, CDCl3) of 3b.

Figure S4. 13C NMR spectrum (100 MHz, CDCl3) of 3b.

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0 ppm

0.904

0.915

1.035

1.071

1.090

1.259

1.333

1.399

1.456

1.472

1.550

1.582

2.471

2.490

2.506

2.567

2.585

2.604

2.616

2.636

2.655

2.824

2.842

2.861

6.853

6.893

7.171

7.210

9.981

12.8

1

32.0

0

2.2

8

4.0

9

1.8

4

0.9

4

0.9

0

1.0

0

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

14.051

14.087

22.543

22.596

26.404

27.112

27.911

29.324

29.759

31.003

31.130

31.517

31.544

31.565

32.257

75.458

118.772

123.091

134.772

140.994

141.569

141.792

146.567

147.727

152.974

181.920

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-2-111 10 9 8 7 6 5 4 3 2 1 0 ppm

-3.042

1.875

2.688

7.352

8.906

8.917

9.348

9.359

10.247

1.8

8

12.7

6

6.3

0

4.2

2

3.8

7

4.0

0

2.1

0

HN

N

N

NH

Figure S5. 1H NMR spectrum (400 MHz, CDCl3) of 5,15-Dimesitylporphyrin.

Figure S6. 13C NMR spectrum (100 MHz, CDCl3) of 5,15-Dimesitylporphyrin.

2030405060708090100110120130140 ppm

21.518

21.723

104.568

117.288

127.856

130.007

131.803

137.627

137.846

139.486

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1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0 ppm

1.854

2.693

7.270

7.351

8.988

8.999

9.406

9.417

10.269

11.5

0

5.6

7

3.9

0

3.9

1

4.0

0

1.8

9N

N

N

N

Zn

Figure S7. 1H NMR spectrum (400 MHz, CDCl3) of [5,15-Dimesitylporphyrinato]

zinc (II).

Figure S8. 13C NMR spectrum (100 MHz, CDCl3) of [5,15-Dimesitylporphyrinato]

zinc (II).

30405060708090100110120130140150 ppm

21.490

21.662

105.506

118.234

127.685

131.258

132.117

137.503

138.781

139.318

149.412

149.832

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N

N

N

N

Br

Br

Zn

Figure S9. 1H NMR spectrum (400 MHz, CDCl3) of [5,15-Dibromo-10,20-

dimesitylporphyrinato] zinc (II).

Figure S10. 13C NMR spectrum (100 MHz, CDCl3) of [5,15-Dibromo-10,20-

dimesitylporphyrinato] zinc (II).

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1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

0.625

1.860

2.680

7.270

7.330

8.787

8.798

9.675

9.686

17.3

0

12.0

3

6.1

6

3.0

6

4.0

8

4.0

0

N

N

N

N

Zn

SiMe3

SiMe3

Figure S11. 1H NMR spectrum (400 MHz, CDCl3) of 2.

Figure S12. 13C NMR spectrum (100 MHz, CDCl3) of 2.

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

0.344

21.480

21.514

100.635

101.497

107.369

120.911

127.725

131.453

131.679

137.641

138.359

139.047

149.947

152.099

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1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

0.757

0.774

0.792

0.932

1.225

1.285

1.303

1.323

1.355

1.367

1.408

1.539

1.585

1.603

1.621

1.887

2.681

2.784

2.802

2.820

2.968

2.986

3.005

7.270

7.334

8.752

8.763

9.154

9.486

9.497

6.5

1

6.5

9

23.4

4

8.7

4

15.0

1

6.5

0

4.1

8

3.9

1

4.0

0

3.2

7

1.6

7

3.3

0NN

NN

Zn

S

C6H13C6H13

OS

C6H13C6H13

O

Figure S13. 1H NMR spectrum (400 MHz, CDCl3) of 4a.

Figure S14. 13C NMR spectrum (100 MHz, CDCl3) of 4a.

2030405060708090100110120130140150 ppm

14.019

14.129

21.515

21.592

22.628

22.656

27.461

28.663

29.413

29.673

30.886

30.917

31.586

31.763

32.328

89.536

100.094

103.129

122.003

127.837

129.360

131.182

131.898

137.324

137.876

138.116

138.995

148.219

150.082

151.631

151.699

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S

C6H13C6H13

NN

NN

Zn

CNS

C6H13C6H13

CNNC

NC

Figure S15. 1H NMR spectrum (400 MHz, CDCl3) of 1a.

Figure S16. 13C NMR spectrum (100 MHz, CDCl3) of 1a.

102030405060708090100110120130140150 ppm

13.988

14.113

21.540

21.652

22.616

28.195

28.771

29.144

29.558

29.732

30.159

30.710

30.901

31.460

31.552

31.712

32.345

75.194

89.439

99.538

106.314

113.874

115.076

122.767

127.935

130.784

131.024

132.254

137.791

138.065

138.924

147.405

147.730

150.321

151.570

154.355

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

0.743

0.760

0.777

0.966

1.271

1.305

1.323

1.343

1.392

1.526

1.545

1.761

1.956

2.712

2.763

2.840

7.371

7.893

8.742

8.752

9.165

6.4

5

6.9

8

23.1

1

13.1

7

4.5

3

12.4

1

5.7

3

8.4

0

4.0

1

2.0

0

4.4

1

3.4

9

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1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.310

1.330

1.341

1.347

1.357

1.386

1.396

1.403

1.441

1.458

1.466

1.486

1.555

1.607

1.626

1.864

1.889

1.914

1.939

2.636

2.653

2.675

2.700

2.727

2.748

2.768

2.774

2.795

2.814

3.026

3.046

3.064

7.061

7.099

7.269

7.303

7.325

7.342

8.722

8.733

9.548

9.559

5.9

1

16.8

1

61.4

9

14.6

3

10.6

1

7.8

5

3.7

7

2.1

1

5.6

5

4.0

0

5.8

9

Figure S17. 1H NMR spectrum (400 MHz, CDCl3) of 4b.

Figure S18. 13C NMR spectrum (100 MHz, CDCl3) of 4b.

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

14.129

14.176

21.478

21.533

22.578

22.660

26.443

27.110

27.494

29.268

29.342

29.352

29.451

29.706

30.940

31.190

31.542

31.597

31.662

31.800

32.254

90.671

100.848

101.166

118.917

118.958

121.511

123.465

127.719

131.059

131.473

134.583

137.288

137.672

138.325

139.032

141.946

142.744

146.942

148.484

149.683

151.593

153.154

181.733

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9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

1.190

1.208

1.228

1.235

1.245

1.264

1.288

1.296

1.304

1.335

1.393

1.402

1.420

1.527

1.545

1.563

1.580

1.853

2.549

2.569

2.594

2.621

2.686

2.705

2.723

2.950

2.968

6.945

6.984

7.193

7.232

7.278

7.687

8.678

8.689

9.460

9.471

6.5

9

18.2

0

54.5

5

8.2

7

13.1

1

13.5

1

4.4

9

3.7

3

2.0

0

2.7

5

4.2

7

1.8

9

3.9

6

3.9

7

S

C6H13 C6H13

S

C6H13 C6H13

NN

NN

Zn S

C6H13C6H13

S

C6H13C6H13

CNNC

NCCN

Figure S19. 1H NMR spectrum (400 MHz, CDCl3) of 1b.

Figure S20. 13C NMR spectrum (100 MHz, CDCl3) of 1b.

2030405060708090100110120130140150 ppm

22.562

22.620

22.631

22.669

26.819

27.479

27.824

29.287

29.318

29.459

29.734

30.935

31.004

31.499

31.557

31.605

31.791

32.170

73.138

90.762

101.192

101.404

114.172

115.592

118.217

120.076

121.720

125.392

127.767

128.297

131.128

131.617

137.220

137.784

138.167

139.009

141.615

144.087

147.248

148.836

149.121

149.762

151.636

155.911

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3500 3000 2500 2000 1500 1000

2173

2854

2919

1650

Tra

nsm

itta

nce

Wavenumber / cm-1

Figure S21. FT-IR spectrum of compound 4a.

4000 3500 3000 2500 2000 1500 1000

1650

2854

2919

Tra

nsm

itta

nce

Wavenumbers /cm-1

Figure S22. FT-IR spectrum of compound 4b.

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3500 3000 2500 2000 1500 1000

1560

2852

2921

2223

2156T

ran

sm

itta

nce

Wavenumber / cm-1

Figure S23. FT-IR spectrum of compound 1a.

3500 3000 2500 2000 1500 1000

1552

2217

2856

2923

Tra

nsm

itta

nce

Wavenumber / cm-1

Figure S24. FT-IR spectrum of compound 1b.

.

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Figure S25. MALDI-MS spectrum of compound 4a (Matrix: Dithranol).

219.0 475.4 731.8 988.2 1244.6 1501.0

Mass (m/z)

0

5174.2

0

10

20

30

40

50

60

70

80

90

100

% I

nte

ns

ity

Voyager Spec #1=>AdvBC(32,0.5,0.1)=>BC=>NR(2.00)=>MC[BP = 1213.9, 5174]

1213.8485

1215.8350

227.0856

1217.8322

1219.8432

304.3328225.0775 1294.8025

239.0742332.4017 668.7840 1290.8050

1203 1208 1213 1218 1223 1228

Mass (m/z)

0

5174.2

0

10

20

30

40

50

60

70

80

90

100

% I

nte

ns

ity

Voyager Spec #1=>AdvBC(32,0.5,0.1)=>BC=>NR(2.00)=>MC[BP = 1213.9, 5174]

1213.8485

1214.8385

1212.8313

1215.8350

1216.8300

1217.8322

1218.8441

1219.8432

1220.8530

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Figure S26. MALDI-MS spectrum of compound 4b (Matrix: Dithranol).

219.0 675.4 1131.8 1588.2 2044.6 2501.0

Mass (m/z)

0

1.5E+4

0

10

20

30

40

50

60

70

80

90

100

% I

nte

ns

ity

Voyager Spec #1=>BC=>AdvBC(32,0.5,0.1)=>NR(2.00)=>BC=>MC[BP = 227.1, 15212]

227.0709

1767.0716

1769.0501225.0551

253.0522

1771.0094

239.0658

242.01701773.0001477.1606

249.01211492.7869 1846.9578

247.0252 1214.6401465.1602 696.69691764.0571

1752.0 1759.4 1766.8 1774.2 1781.6 1789.0

Mass (m/z)

0

1.3E+4

0

10

20

30

40

50

60

70

80

90

100

% I

nte

ns

ity

Voyager Spec #1=>BC=>AdvBC(32,0.5,0.1)=>NR(2.00)=>BC=>MC[BP = 227.1, 15212]

1767.0716

1768.06381766.0862

1769.0501

1765.0923

1770.0395

1771.0094

1772.0225

1773.0001

1773.9424

1764.0571

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19

Figure S27. MALDI-MS spectrum of compound 1a (Matrix: Dithranol).

219.0 775.4 1331.8 1888.2 2444.6 3001.0

Mass (m/z)

0

8132.3

0

10

20

30

40

50

60

70

80

90

100

% I

nte

ns

ity

Voyager Spec #1=>NR(1.00)=>BC=>MC[BP = 227.1, 8132]

227.0706

1310.7982

253.0846

1313.7500239.0742

311.3001668.6991430.4138

242.0540 640.6737477.1787

460.1171264.0184 697.7461 933.0082

1301.0 1306.4 1311.8 1317.2 1322.6 1328.0

Mass (m/z)

0

3205.2

0

10

20

30

40

50

60

70

80

90

100

% I

nte

ns

ity

Voyager Spec #1=>NR(1.00)=>BC=>MC[BP = 227.1, 8132]

1310.7982

1309.8026

1308.8173

1311.7884

1312.7648

1313.7500

1314.7669

1315.7697

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20

Figure S28. MALDI-MS spectrum of compound 1b (Matrix: Dithranol).

219.0 675.4 1131.8 1588.2 2044.6 2501.0

Mass (m /z)

0

3135.5

0

10

20

30

40

50

60

70

80

90

100

% Inte

nsity

Voyager Spec #1=>NR(1.00)=>BC=>AdvBC(32,0.5,0.1)=>MC[BP = 1766.9, 3135]

1767.0188

1768.9655

227.0699

1771.9359225.0592

242.2479

1774.0295253.1001

1488.7857323.0891

1756.0 1761.6 1767.2 1772.8 1778.4 1784.0

Mass (m/z)

0

3135.5

0

10

20

30

40

50

60

70

80

90

100

% I

nte

ns

ity

Voyager Spec #1=>NR(1.00)=>BC=>AdvBC(32,0.5,0.1)=>MC[BP = 1766.9, 3135]

1767.0188

1768.0294

1768.9655

1766.0422

1769.9983

1765.0705

1770.9569

1771.9359

1772.9963

1774.0295

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21

3. Thermogravimetric analysis

200 400 600 800 1000

40

50

60

70

80

90

100

110

T = 369 ºC

We

igh

t / %

T / ºC

1a

200 400 600 800 1000

20

30

40

50

60

70

80

90

100

110

T = 374 ºC

We

igh

t / %

T / ºC

1b

Figure S29. Thermogravimetric analysis of 1a and 1b.

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22

4. UV-Visible and emission spectroscopies

400 500 600 700 800 900

0,0

0,2

0,4

0,6

0,8

1,0

Ab

so

rban

ce / a

. u

.

Wavenumber / nm

2

4a

1a

Figure S30. Normalized UV-Vis absorption spectra of compounds 1a and precursors 2, 4a in dichloromethane.

400 500 600 700 800 900

0,0

0,2

0,4

0,6

0,8

1,0

Ab

so

rban

ce / a

. u

.

Wavenumber / nm

2

4b

1b

Figure S31. Normalized UV-Vis absorption spectra of compounds 1b and precursors 2 and 4b in dichloromethane.

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23

400 500 600 700 800 900

0,0

0,2

0,4

0,6

0,8

1,0

Ab

so

rban

ce / a

. u

.

Wavenumber / nm

1a

1b

Figure S32. Normalized absorption spectra of 1a (--) and 1b () in dichloromethane solution (10-5 M).

5.

Figure S33. Emission spectra of compound 1b and 4b in dichloromethane (10-5 M).

600 650 700 750 800 850 900

0

100

200

300

400

500

600

Inte

nsity / a

.u.

wavelength / nm

4b

1b exc

= 486

1b exc

= 540

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6. Square Wave plots

Compound 2TV Compound 2

Compound 1a Compound 1b

Figure S34. Cyclic Voltammetry of compound 1a-b and 2TV and 2 (referred to

Fc/Fc+).

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

-1.0x10-5

0.0

1.0x10-5

2.0x10-5

3.0x10-5

4.0x10-5

5.0x10-5

I/m

A

E/V

2TV

-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

-6.0x10-6

-4.0x10-6

-2.0x10-6

0.0

2.0x10-6

4.0x10-6

6.0x10-6

8.0x10-6

1.0x10-5

1.2x10-5

1.4x10-5

I/m

A

E/V

2

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

-8.0x10-6

-6.0x10-6

-4.0x10-6

-2.0x10-6

0.0

2.0x10-6

4.0x10-6

6.0x10-6

8.0x10-6

1.0x10-5

1.2x10-5

I/m

A

E/V

1a

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

-2.0x10-6

0.0

2.0x10-6

4.0x10-6

6.0x10-6

8.0x10-6

I/m

A

E/V

1b

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25

Compound 2TV

Compound 2

Compound 1a Compound 1b

Figure S35. Cyclic Voltammetry of compound 1a and 1b and the precursors 2TV

and 2 (referred to Fc/Fc+).

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

1.0x10-5

2.0x10-5

I/m

A

E/V

2TV

-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0

0.0

2.0x10-6

4.0x10-6

6.0x10-6

8.0x10-6

1.0x10-5

1.2x10-5

1.4x10-5

1.6x10-5

I/m

A

E/V

2

-0.2 0.0 0.2 0.4 0.6 0.8 1.0

0.0

2.0x10-6

4.0x10-6

6.0x10-6

8.0x10-6

1.0x10-5

1.2x10-5

I/m

A

E/V

1a

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

0.0

2.0x10-6

4.0x10-6

I/m

A

E/V

1b

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26

7. EQE and J-V characteristics for 1a:PC71BM (1:2)

Figure S36. EQE (a) and J-V (b) characteristics of the SMBHJ for 1a blending with

PC61BM and PC71BM in a 1:2 ratio.