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Systematic elongation of thienyl linkers and their effect on optical and

electrochemical properties in Carbazole-BODIPY donor-acceptor systems

Alina Brzeczek, Katarzyna Piwowar, Wojciech Domagala, Mikołaj M. Mikołajczyk,

Krzysztof Walczak, Pawel Wagner

Electronic Supporting Information

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

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Scheme SI.1. Synthetic route for the preparation of aldehydes 2–5. Reagents and conditions: (i) POCl3, DMF, (ii)18-Crown-6,

K2CO3, CH2Cl2, reflux, 1,5h; (iii) TFA, CH2Cl2, H2O, r.t., 0,5h.

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Figure SI.1 1H and

13C NMR spectra of aldehydes 2, 3, 4, 5.

2

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3

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4

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5

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Figure SI.2 1H and

13C NMR spectra of dyes I, II, III, IV, V.

Dye I

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Dye II

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Dye III

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Dye IV

DYE V

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Table SI.1. Formal potentials and peak-to-peak separation parameter of redox pairs of dyes I to V computed from cyclic

voltammograms presented in figure 8. Due to close overlap of redox peaks of dyes II to V in the positive

potentials’ segment, meaningful determination of experimental formal potentials of redox pairs involved is

unfeasible.

Dye E0’

[V]

ΔE’pp

[mV]

E0’’

[V]

ΔE’’pp

[mV]

E0’’’

[V]

ΔE’’’pp

[mV]

I -1.52 88 0.22 77 0.47 77

II -1.57 143 - - - -

III -1.39 113 - - - -

IV -1.31 80 - - - -

V -1.66 132 - - - -

Table SI.2. Conjugation ratio expressing the number of atoms contributing their atomic orbitals to a given molecular orbital,

to the total number of atoms in a molecule, set against ionization potentials and electron affinities of all

investigated dyes.

Dye Conjugation ratio for: IP

[eV]

EA

[eV] HOMO LUMO

I 0.867 0.474 5.24 3.65

II 0.760 0.438 5.28 3.67

III 0.893 0.408 5.22 3.76

IV 0.793 0.379 5.27 3.84

V 0.698 0.515 5.32 3.53

a)

0.65 0.70 0.75 0.80 0.85 0.90 0.955.20

5.22

5.24

5.26

5.28

5.30

5.32

5.34

V

II

IV

I

III

Ioniz

ation P

ote

ntial (I

P)

HOMO conjugation ratio

b)

0.35 0.40 0.45 0.50 0.553.50

3.55

3.60

3.65

3.70

3.75

3.80

3.85

3.90

IV

III

III

V

Ele

ctr

on A

ffin

ity (

EA

)

LUMO conjugation ratio

Figure SI.3. Correlation plots of characteristic electron transfer energies with conjugation ratio of given frontier molecular

orbitals for dyes I through V: a) Ionization Potential vs HOMO, b) Electron Affinity vs LUMO.

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Figure SI.4 Contours of selected molecular orbitals of neutral and singly charged states of dye: a) I, b) II, c) III, d) IV, e) V

a) Dye I

Radical cation Neutral molecule Radical anion

No. E

[a.u.] No.

E

[a.u.] No.

E

[a.u.]

LU

MO

+1

199

0.0

104

3

200

0.0

943

7

LU

MO

198

-0.1

55

30

198

-0

.054

72

199

0.0

928

4

SO

MO

197

-0.3

06

94

198

-0.0

57

13

HO

MO

196

-0.3

21

88

197

-0.2

04

03

197

-0.1

10

75

HO

MO

-1

196

-0.2

34

64

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b) Dye II

Radical cation Neutral molecule Radical anion

No. E

[a.u.] No.

E

[a.u.] No.

E

[a.u.]

LU

MO

+1

255

-0.0

20

92

LU

MO

254

-0.1

51

40

254

-0.0

64

17

255

0.0

572

8

SO

MO

253

-0.2

83

29

254

-0.0

70

56

HO

MO

252

-0.2

89

63

253

-0.1

99

75

253

-0.1

16

98

HO

MO

-1 251

-0.3

11

87

252

-0.2

20

50

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c) Dye III

Radical cation Neutral molecule Radical anion

No. E

[a.u.] No.

E

[a.u.] No.

E

[a.u.]

LU

MO

+1

283

-0.0

27

17

284

0.0

514

4

LU

MO

282

-0.1

52

71

282

-0

.067

06

283

0.0

469

8

SO

MO

281

-0.2

80

77

282

-0.0

73

60

HO

MO

280

-0.2

85

25

281

-0.2

01

44

281

-0.1

19

93

HO

MO

-1

279

-0.3

07

43

280

-0.2

19

33

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d) Dye IV

Radical cation Neutral molecule Radical anion

No. E

[a.u.] No.

E

[a.u.] No.

E

[a.u.]

LU

MO

+1

297

-0.0

29

65

298

0.0

429

8

LU

MO

296

-0.1

51

38

296

-0

.067

39

297

0.0

402

5

SO

MO

295

-0.2

74

12

296

-0.0

74

14

HO

MO

294

-0.2

76

85

295

-0.2

00

55

295

-0.1

20

23

HO

MO

-1

293

-0.2

99

71

294

-0.2

15

56

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e) Dye V

Radical cation Neutral molecule Radical anion

No. E

[a.u.] No.

E

[a.u.] No.

E

[a.u.]

LU

MO

+1

339

-0.0

36

48

340

0.0

270

3

LU

MO

338

-0.1

53

04

338

-0

.069

85

339

0.0

250

9

SO

MO

337

-0.2

64

89

338

-0.0

77

12

HO

MO

336

-0.2

66

51

337

-0.2

02

40

337

-0.1

23

05

HO

MO

-1

335

-0.2

91

00

336

-0.2

13

77