Supporting Information (53 pages) Table of Contents Pages fileHeiser, 3 Pascal Retailleau, 4 Sandra Rihn, 1 Antoine Mirloup, 1 and Raymond Ziessel 1 Supporting Information (53 pages)

S1

High Performance Solution-processed Solar Cells and Ambipolar behavior

in OFETs with Thienyl-BODIPY Scaffoldings

Thomas Bura,1 Nicolas Leclerc,2 Sadiara Fall3 Patrick Lévêque,3 Thomas Heiser,3 Pascal Retailleau,4 Sandra Rihn,1 Antoine Mirloup,1 and Raymond

Ziessel1

Supporting Information (53 pages)

Table of Contents Pages

1) General Methods S1

2) Synthetic Experimental Part S2

3) NMR Spectra traces S10

4) DSC traces for TB1-4 S39

5) X-ray diffraction data for TB2 S41

6) Atomic force microscopy investigations S41

7) Absorption and Fluorescence Spectra and Data (Table S1) S44

8) Cyclic voltammetry traces and Data (Table S2) S48

9) Devices preparation and charge mobilities (Table S3 + S4) S49

10) Additional References S53

1) General Methods All reactions were performed under an atmosphere of dried argon using standard Schlenk tube

techniques. All chemicals were used as received from commercial sources unless stated

otherwise. CH2Cl2 was distilled from P2O5 under an argon atmosphere. THF was distilled

from sodium and benzophenone under an Ar atmosphere. DMF was distilled from KOH

under an argon atmosphere. 1H NMR (300.1 MHz) and 13C NMR (75.5 MHz) spectra were

recorded at room temperature (rt) on a Bruker Advance 300 MHz spectrometer, 1H NMR

(200.1 MHz) and 13C NMR (50.5 MHz) spectra were recorded at rt on a Bruker Advance 200

MHz spectrometer using perdeuteriated solvents as internal standards. Chromatographic

purifications were performed using silica gel (40-63 µm). TLC was performed on silica gel

plates coated with fluorescent indicator.

S2

Absorption spectra were recorded on a Schimadzu UV-3000 absorption spectrometer. The

steady-state fluorescence emission and excitation spectra were obtained by using a HORIBA

JOBIN YVON FLUOROMAX 4. All fluorescence spectra were corrected. The fluorescence

quantum yield (φexp) was calculated from eq 1.1

(1)

Here, I denotes the integral of the corrected emission spectrum, OD is the optical density at

the excitation wavelength and η is the refractive index of the medium. The reference systems

used were rhodamine 6G (φref = 0.78) in air equilibrated water and

Tetramethoxydiisoindomethene-difluoroborate (φref = 0.51). 2 Luminescence lifetimes were

measured on an Edimburgh Instruments spectrofluorimeter equipped with a R928

photomultiplier and a PicoQuant PDL 800-D pulsed diode connected to a GwInstect GFG-

8015G delay generator. No filter was used for the excitation. Emission wavelengths were

selected by a monochromator. Lifetimes were deconvoluted with FS-900 software using a

light-scattering solution (LUDOX) for instrument response.

2) Synthetic Experimental Part All reagents thiophene, 2-bromothiophene, 2-(5-hexylthiophen-2-yl)thiophene, -(2-

methoxyethoxy)ethanol, 2-thienylethanol, were used directly as obtained commercially unless

otherwise noted. Compound 1,3 2,4 3,5 4,6 9,7 128 were prepared according to the respective

references.

General procedure A for the Vilsmeier reaction: In a Schlenk tube containing anhydrous

DMF at 0° was added 1.2 equivalent of POCl3. The mixture was stirred and then gradually

warmed at room temperature over a period of 1h. The thiophene derivative was added in the

mixture and then heated at 60°C during 12h. The solution was poured into ice-water. The pH

was adjusted to 7 with sodium hydroxide solution. The reaction mixture was extracted with

ether. The organic layer was washed three times with water and dried over MgSO4 or

absorbent cotton and the solvent was evaporated under reduced pressure and purified by

silica-gel column chromatography to afford the desired compound.

S3

General procedure B for the Knoevenagel condensation: In a round bottom flask equipped

with a Dean stark apparatus, thienyl-aldehyde 2.2 eq , piperidine (2 mL) and a crystal of p-

TsOH were added to a stirred solution of BODIPY (1eq) in toluene (20mL). The solution

was heated at reflux during 12 hours. After cooling to room temperature, the mixture was

washed three times with water. The organic phase was dried over MgSO4 or absorbent cotton

and the solvent was evaporated under reduced pressure. The resulting crude residue was

purified by silica-gel column chromatography to afford the desired compound.

Scheme S1: Synthesis of compound TB1.

NB

NFF

S S

I

NB

NFF

I

O

SToluene, piperidine

pTsOH

POCl3

DMF

S+

3

S

H

BuLi, THF

Bromohexyl

1 2 TB1

2-Hexylthienyl (1). The purification was carried out by chromatography on flash silica as

static phase with a mixture of petroleum ether as mobile phase and afforded 1 (92%). 1H

NMR (CDCl3, 300 MHz): 0.88-0.93 (m, 3H), 1.29-1.40 (m, 6H), 1.64-1.74 (m, 2H), 2.83 (t,

2H, 3J = 7.7 Hz), 6.78-6.79 (m, 1H), 6.91-6.94 (m, 1H), 7.11-7.12 (m, 1H).

5-Hexylthienyl-2-carbaldehyde (2). The purification was carried out by chromatography on

flash silica as static phase with a mixture of dichloromethane/petroleum ether 30/70 as mobile

phase and afforded 2 (61%). 1H NMR (CDCl3, 300 MHz): 0.85-0.90 (m, 3H), 1.24-1.41 (m,

6H), 1.64-1.74 (m, 2H), 2.86 (t, 2H, 3J = 7.6 Hz), 6.88-6.90 (m, 1H), 7.59-7.60 (m, 1H), 9.80

(s, 1H).

TB1 was prepared according to the general procedure B from 434.3 mg (0.965 mmol) of

compound 3 and 282.5 mg (1.439 mmol) of 5-hexylthienyl-2-carbaldehyde (2) dissolved in

toluene (20 mL). The purification was carried out by chromatography on flash silica as static

phase with a mixture of toluene/dichloromethane/petroleum ether (35/5/60) as mobile phase

and afforded TB1 as a dark purple powder (196.1 mg 25%). 1H NMR (CDCl3, 300 MHz):

0.88-0.93 (m, 6H), 1.33-1.42 (m, 12H), 1.45 (s, 6H), 1.67-1.74 (m, 4H), 2.83 (t, 4H, 3J = 7.6

Hz), 6.56 (s, 2H), 6.72 (s, 1H), 6.73 (s, 1H), 7.03 (s, 1H), 7.05 (s, 1H), 7.08 (d, 2H, 3J = 8.1

Hz), 7.27-7.42 (m, 4H), 7.84 (d, 2H, 3J = 8.1 Hz). 13C NMR (CDCl3, 75 MHz): 14.2, 14.8,

S4

15.0, 22.7, 28.9, 29.8, 30.8, 31.6, 31.7, 95.0, 117.2, 117.9, 121.4, 125.4, 129.0, 130.0, 130.4,

131.5, 132.8, 134.9, 138.1, 138.4, 140.1, 142.0, 142.4, 149.3, 153.3, 155.2. EI-MS, m/z (%):

806.1 ([M], 100). Anal. Calcd for C41H46BF2IN2S2 (Mr = 806.66): C, 61.05; H, 5.75; N, 3.47

Found: C, 60.81; H, 5.44; N, 3.21.


NB

NFF

S S

S S

I

NB

NFF

I

O

S

S

H

Toluene, piperidine

pTsOH

POCl3

DMF

S

S+

3 TB24

5-(5-Hexylthienyl-2-yl)thiophene-2-carbaldehyde (4). The purification was carried out by

chromatography on flash silica as static phase with a mixture of CH2Cl2/petroleum ether

(50/50) as mobile phase and afforded 4 as an yellow oil (1.1 g, 98 %).1H NMR (CDCl3, 200

MHz): 0.9 (t, 3H, 3J = 6.7Hz), 1.27-1.42 (m, 6H), 1.62-1.73 (m, 2H), 2.82 (t, 2H, 3J = 7.6Hz),

6.75 (d, 1H, 3J = 3.4 Hz), 7.16-7.20 (m, 2H), 7.65 (d, 1H, 3J = 3.9 Hz), 9.84 (s, 1H).

TB2 was prepared according to the general procedure B from 310 mg (0.68 mmol) of

compound 3 and 421 mg (1.51 mmol) of 5-(5-hexylthienyl-2-yl)thiophene-2-carbaldehyde

(4). The purification was carried out by chromatography on flash silica as static phase with a

mixture of dichloromethane/toluene/petroleum ether (20/30/50) as mobile phase and afforded

TB2 as a dark purple powder (460 mg, 70%). 1H NMR (CDCl3, 300 MHz): 0.91 (t, 6H, 3J =

6.6Hz), 1.26-1.43 (m, 12H), 1.47 (s, 6H), 1.69 (m, 4H), 2.82 (t, 4H, 3J = 7.4 Hz), 6.60 (s, 2H),

6.73 (d, 2H, 3J = 3,3 Hz), 7.04-7.12 (m, 8H), 7.30 (overlapping with solvent d, 2H, 3J = 16.0

Hz), 7.45 (d, 2H, 3J = 16.0 Hz), 7.85 (d, 2H, 3J = 8.1 Hz). 13C NMR (CDCl3, 50 MHz): 14.2,

15.1, 22.7, 28.9, 30.4, 31.7, 94.5, 118.0, 118.3, 123.9, 124.4, 125.2, 129.1, 129.8, 130.8,

133.6, 134.8, 135.0, 135.8, 138.4, 140.1, 140.7, 141.5, 146.6, 152.3. EI-MS, m/z (%): 970.1

([M], 100). Anal. Calcd for C49H50BF2IN2S4 (Mr = 970.91): C, 60.62; H, 5.19; N, 2.89;

Found: C, 60.52 ; H, 4.97 ; N, 2.70.

S5


HOO

O

NaH, CuI, Pyridine

S O O O S O O OSn

nBuLi, SnMe3Cl

S O O OS

S Br

Pd(PPh3)4, THF

5 6

S Br THF

POCl3

DMF

S O O OS

O

H NB

NFF

I

NB

NFF

S S

S S

O

O

O

O

I

OO

Toluene, piperidine

pTsOH

7

8 3 TB3

+

2-(2-(2-Methoxyethoxy)-ethoxy)thiophene (5):

Copper iodide (12.2 mmol) and sodium hydride (92 mmol) were added to a solution of 2-(2-

methoxyethoxy)ethanol (0.3 mol) in 20 mL of dry pyridine and allowed to stir 30 min at rt.

2-bromothiophene (61 mmol) was then added and the mixture was heated at 100°C for 7

days. The mixture was slowly cooled down to rt and then poured into a water-CH2Cl2

mixture. Then, the organic solution was extracted three times with HCl 10% to remove

pyridine and then water. The CH2Cl2 organic phase was dried over Na2SO4 and concentrated

under vacuum. The purification was carried out by chromatography on flash silica as static

phase with a mixture of cyclohexane / ethyl acetate (80/20) as mobile phase and afforded 5 as

an uncoloured oil (4.2 g, 34%). 1H NMR (CDCl3 300 MHz): 3.39 (s, 3H), 3.58 (dd ; 3J = 4.98 Hz, 3J = 6.39 Hz, 2H), 3.71

(dd ; 3J = 5.0 Hz, 3J = 6.36 Hz, 2H), 3.84 (t, 3J = 4.7 Hz, 2H), 4.2 (t, 3J = 4.7 Hz, 2H), 6.24

(dd, 3J = 5.82 Hz, 4J = 1.35 Hz, 1H), 6.55 (dd, 3J = 3.69 Hz, 4J = 1.29 Hz, 1H), 6.70 (q, 3J =

5.76 Hz, 3J = 3.75 Hz, 1H). 13C NMR (CDCl3, 50 MHz): 59.1, 69.4, 70.8, 71.9, 73.1, 105.2,

112.2, 124.6, 165.3. EI-MS, m/z (%): 202.1 ([M], 100). Anal. Calcd for C9H14O3S

(Mr = 202.27): C, 53.44; H, 6.98; Found C, 53.25; H, 6.84.

2-Trimethyltin-5-(2-(2-methoxyethoxy)-ethoxy)thiophene (6):

To a solution of compound 5 (13.8 mmol) in dry THF (40 mL) at -78°C, a solution of 2.5 M

of nBuLi in hexane (15.2 mmol) was added slowly. The resulting solution was then stirred at

S6

-78°C for 1h and then a 1.0 M solution of trimethyltin chloride in THF (18 mmol) was added.

The solution was warmed to rt and stirred overnight. Then the solution was poured into water

and extracted with ethylacetate. The organic layer was washed three times with water and

dried over Na2SO4. The organic layer was then concentrated under vacuum. The crude

product is used without further purification. 1H NMR (CDCl3, 300 MHz): 0.32 (s, 9H), 3.39 (s, 3H), 3.58 (dd, 3J = 4.89 Hz, 3J = 6.36 Hz,

2H), 3.71 (dd, 3J = 4.95 Hz, 3J = 6.45 Hz, 2H), 3.84 (t, 3J = 4.98 Hz, 2H), 4.21 (t, 3J = 4.65 Hz,

2H), 6.37 (d, 3J = 3.42 Hz, 1H), 6.79 (d, 3J = 3.51 Hz, 1H). 13C NMR (CDCl3, 50 MHz): -8.3,

59.1, 69.5, 70.8, 72.0, 73.2, 107.1, 123.0, 133.2, 170.7.

5-(2-(2-Methoxyethoxy)-ethoxy)-2,2’-bithiophene (7):

Compound 6 (6.7 mmol) and 2-bromothiophene (6.1 mmol) were dissolved in 25 mL of dry

THF and the solution was degassed with argon. Then, [Pd(PPh3)4] in catalytic amount was

added and the reaction mixture was stirred at 80°C for 48 hours under argon atmosphere.

Then, the solution was cooled to rt and filtered onto a celite pad. The organic layer was

washed three times with water and concentrated under reduced pressure. The purification was

carried out by chromatography on flash silica as static phase with a mixture of cyclohexane /

ethyl acetate (80/20) as mobile phase and afforded 7 as a pale yellow oil (1.23 g, 65%). 1H NMR (Acetone d6, 300 MHz): 3.31 (s, 3H), 3.52 (dd, 3J = 5.49 Hz, 3J = 6.66 Hz, 2H), 3.64

(dd, 3J = 5.04 Hz, 3J = 6.18 Hz, 2H), 3.81 (m, 2H), 4.24 (m, 2H), 6.28 (d, 3J = 3.90 Hz, 1H),

6.89 (d, 3J = 3.87 Hz, 1H), 7.03 (q, 3J = 5.10 Hz, 3J = 5.13 Hz, 1H), 7.09 (dd, 3J = 3.54 Hz, 4J=1.08 Hz, 1H), 7.31 (dd, 3J = 5.10 Hz, 4J = 1.17 Hz, 1H). 13C NMR (Acetone d6, 50 MHz):

58.8, 69.9, 71.2, 72.7, 74.1, 106.6, 122.4, 123.2, 124.4, 124.5, 128.7, 138.6, 165.3. EI-MS,

m/z (%): 284.1 ([M], 100). Anal. Calcd for C13H16O3S2 (Mr = 284.39): C, 54.90; H, 5.67;

Found: C, 54.68; H, 5.74.

5-(5-(2-(2-Methoxyethoxy)ethoxy)thiophen-2-yl)thienyl-2-carbaldehyde (8) was prepared

according to the general procedure A from 600 mg of 7 (2.11 mmol) and 0.3 mL of POCl3

(3.16 mmol). The purification was carried out by chromatography on flash silica as static

phase with a mixture of petroleum ether/ethyl acetate (50/50) as mobile phase to give an

yellow oil (480mg, 70%). 1H NMR (CDCl3, 200 MHz): 3.39 (s, 3H), 3.55-3.60 (m, 2H), 3.67-

3.72 (m, 2H), 3.83-3.87 (m, 2H), 4.22-4.26 (m, 2H), 6.21 (d, 1H, 3J = 4.1 Hz), 7.01-7.05 (m,

2H), 7.61 (d, 1H, 3J = 4.1 Hz), 9.80 (s, 1H). 13C NMR (CDCl3, 50 MHz): 59.2, 69.4, 71, 72.1,

73.3, 106.6, 122.6, 122.8, 124.6, 137.7, 140.5, 148.4, 166.9, 182.4. EI-MS, m/z (%): 312.1

([M], 100). Anal. Calcd for C14H16O4S2 (Mr = 312.4): C, 53.82; H, 5.16; Found: C, 53.69; H,

5.04.

S7

TB3 was prepared according to the general procedure B from 165 mg (0.36 mmol) of 3 and

250 mg (0.8 mmol) of 5-(5-(2-(2-methoxyethoxy)ethoxy)thiophen-2-yl)thiophene-2-

carbaldehyde. The purification was carried out by chromatography on flash silica as static

phase with a mixture of dichloromethane/ethyl acetate (80/20) as mobile phase to afford TB3

as a dark purple powder (510 mg, 62%). 1H NMR (CDCl3,300 MHz): 1.47 (s, 6H), 3.41 (s,

6H), 3.58-3.61 (m, 4H), 3.71-3.74 (m, 4H), 3.86-3.89 (m, 4H), 4.24-4.27 (m, 4H), 6.22 (d,

2H, 3J = 4 Hz), 6.59 s, 2H), 6.93-6.95 (m, 4H), 7.07-7.10 (m, 4H), 7.29 (overlapping with

solvent d, 2H, 3J = 16 Hz), 7.43 (d, 2H, 3J = 16 Hz), 7.85 (d, 2H, 3J = 8.2 Hz). EI-MS, m/z

(%): 1038.1 ([M], 100). Anal. Calcd for C47H46BF2IN2O6S4 (Mr = 1038.85): C, 54.34; H,

4.46 ; N, 2.70; Found: C, 54.17; H, 4.38; N, 2.52.


S Sn +S O O OI S O O O

S

Pd2dba3, P(o-tolyl)3 13

Toluene

SO

O

OO

OS

OH

NaH

THF

SO

O O+S

OO O

II2

HgO, benzene

OS

S OO

OH

POCl3

DMF

NB

NFF

I

Toluene, piperidine

pTsOH

O

S

S

O

O

O

H

+ NB

NFF

S S

S S

O

O

O

O

I

O O

TB4

3

9 10 11

12 14

Compound 9 : The purification was carried out by chromatography on flash silica as static

phase with a mixture of ethyl acetate/petroleum ether (50/50) as mobile phase and afforded 9

as an colorless oil. 1H NMR (CDCl3, 200 MHz): 2.45 (s, 3H), 3.35 s, 3H), 3.46-3.50 (m, 2H),

3.56-3.61 (m, 2H), 3.67-3.72 (m, 2H), 4.15-4.20 (m, 2H), 7.34 (d, 2H, 3J = 7.7 Hz), 7.80 (d,

2H, 3J = 8.2 Hz).

2-(2-(2-(2-Methoxyethoxy)ethoxy)ethyl)thiophene (10).

To a slurry of NaH (60 % in paraffine oil, 73 mg, 1.82 mmol) in anhydrous THF (5 mL), 2-

thienylethanol (260 µL, 1.56 mmol) was added under argon. The mixture was stirred at rt for

S8

45 min. Then the tosylate 9 (356 mg, 1.30 mmol) was dropwise added and the reaction

allowed to stir overnight. The reaction mixture at 0 °C was neutralized by a slow addition of 1

M solution of HCl, washed with H2O, extracted with ethyl acetate, dried over MgSO4 and

concentrated under reduced pressure. The purification was carried out by chromatography on

flash silica as static phase with a mixture of petroleum ether/ethyl acetate (8:2) as mobile

phase and afforded 10 (228.0 mg, 76%) as an yellow oil. 1H NMR (300 MHz, (CD3)2CO)

7.23 (dd, 1H, 3J = 5.1 Hz, 4J = 1.2 Hz), 6.93-6.90 (m, 2H), 3.67 (t, 2H, 3J = 6.6 Hz), 3.59-3.55

(m, 6H), 3.48-3.45 (m 2H), 3.28 (s, 3H), 3.06 (t, 2H, 3J = 6.6Hz). 13C NMR (75 MHz, CDCl3)

142.4, 127.4, 126.0, 125.9, 124.2, 72.7, 72.4, 71.2, 71.1, 71.0, 58.8, 31.0. EI-MS, m/z (%):

230.1 (100). Anal. Calcd for C11H18O3S (Mr = 230.32) C, 57.36; H, 7.88. Found: C, 57.01; H,

7.53.

1-(5-(2-(2-(2-Methoxyethoxy)ethoxy)ethyl)thiophen-2-yl)ethanone (11).

To a solution of 2-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)thienyl (2.47g, 10.73 mmol) in

benzene (110 mL) was added in small portions of mercuric oxide (2.44g, 11.27 mmol), and

iodine ( 2.86g, 11.27 mmol) at 0°C. The mixture was stirred for 4h at rt and then filtered

through a Celite pad. The filtrate was poured into water, and the aqueous layer was extracted

with ether. The organic extracts were washed with 5% aqueous Na2S2O3 and dried over

magnesium sulfate. The organic phase was concentrated under reduced pressure. The

purification was carried out by chromatography on flash silica as static phase with a mixture

of petroleum ether and ethyl acetate (6:4) as mobile phase to afford compound 11 (3.35 g,

87%) as a yellow oil. 1H NMR (200 MHz, CDCl3) 7.04 (d, 1H, 3J = 3.3 Hz), 6.54 (d, 1H, 3J =

3.3 Hz), 3.70-3.63 (m, 10H), 3.57-3.53 (m, 2H), 3.88 (s, 3H), 3.07 (t, 2H, 3J = 6.6 Hz). 13C

NMR (75.4 MHz, (CD3)2CO) 149.4, 137.5, 128.1, 126.0, 72.7, 71.9, 71.2, 71.1, 71.0, 58.9,

31.5. EI-MS, m/z (%): 356.0 (100). Anal. Calcd for C11H17IO3S (Mr = 356.22): C, 37.09; H,

4.81. Found: C, 36.90; H, 4.62.

Compound 12 : The crude product is used without further purification. 1H NMR (CDCl3, 300

MHz): 0.40 (s, 9H), 7.24-7.29 (overlapping with solvent m, 2H), 7.66-7.67 (m, 1H).

5-(2-(2-(2-Methoxyethoxy)ethoxy)ethyl)-2,2'-bithiophene (13):

2-trimethyltinthiophene (12) (1.68 mmol), 2-iodo-5-(2-(2-(2-methoxyethoxy)ethoxy)

ethyl)thiophene (0.9 mmol) and tri(o-tolyl)phosphine (67.5µmol) were dissolved in 5 mL of

dry toluene and the solution was degased with argon. Then, [Pd2dba3] (17.5 µmol) in catalytic

amount was added and the reaction mixture was stirred at 110°C for 24 hours under argon

atmosphere. Then, the solution was cooled to room temperature and filtered onto a celite pad.

S9

The organic layer was washed three times with water and concentrated under reduced

pressure. The purification was carried out by chromatography on flash silica as static phase

with a mixture of cyclohexane / ethyl acetate (80/20) as mobile phase to afford compound 11

as a pale yellow oil (177 mg, 63%). 1H NMR (CDCl3, 300 MHz): 3.07 (t, 2H, 3J = 6.8 Hz), 3.85 (s, 3H), 3.53-3.57 (m, 2H), 3.63-

3.76 (m, 8H), 6.74-6.76 (m, 1H), 6.97-7.01 (m, 2H), 7.09-7.11 (m, 1H), 7.16-7.19 (m, 1H).

13C NMR (CDCl3, 50 MHz): 30.7, 59.12, 70.5, 70.7, 71.8, 72.1, 123.2, 123.5, 123.9, 126,

127.7, 135.7, 137.9, 140.8. EI-MS, m/z (%): 312.1 ([M], 100). Anal. Calcd for C13H16O3S2

(Mr = 312.45): C, 57.66; H, 6.45; Found: C, 57.52; H, 6.51.

Compound 14 was prepared according to the general procedure A from 150 mg of 13 (0.476

mmol) and 66.6 µL of POCl3 (0.715 mmol). The purification was carried out by

chromatography on flash silica as static phase with a mixture of petroleum ether/ethyl acetate

(50/50) as mobile phase to give 14 as an yellow oil (91 mg, 56%). 1H NMR (200 MHz,

CDCl3) 9.80 (s, 1H), 7.61 (d, 1H, 3J = 4.0 Hz), 7.13-7.16 (m, 2H), 6.78 (d, 1H, 3J = 3.6 Hz),

3.73-3.60 (m, 8H), 3.54-3.50 (m, 2H), 3.35 (s, 3H), 3.06 (t, 2H, 3J = 6.4 Hz). 13C NMR (75

MHz, CDCl3) 182.5, 147.7, 144.2, 141.1, 137.5, 134.2, 126.6, 126.0, 123.6, 71.9, 71.3, 70.6,

70.4, 59.0, 30.8. EI-MS, m/z (%): 340.1 ([M], 100). Anal. Calcd for C16H20O4S2

(Mr = 340.46): C, 56.44; H, 5.92; Found: C, 56.21; H, 5.74.

TB4 was prepared according to the general procedure B from 55 mg (0.12 mmol) of 3 and 90

mg (0.27 mmol) of 5-(5-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)thiophen-2-yl)thiophene-2-

carbaldehyde. The purification was carried out by chromatography on flash silica as static

phase with a mixture of dichloromethane/ethyl acetate (80/20) as mobile phase to afford TB4

as a dark purple powder. 1H NMR (CDCl3, 300 MHz): 1.47 (s, 6H), 3.10 (t, 4H, 3J = 6.7 Hz),

3.39 (s, 6H), 3.55-3.58 (m, 4H), 3.66-3.69 (m, 12H), 3.75 (t, 4H, 3J = 6.7 Hz), 6.60 (s, 2H),

6.80 (d, 2H, 3J = 3.6 Hz), 7.05-7.14 (m, 8H), 7.30 (overlapping with solvent d, 2H, 3J = 16,0

Hz), 7.45 (d, 2H, 3J = 16.0 Hz), 7.85 (d, 2H, 3J = 8.2 Hz). 13C NMR (CDCl3, 50 MHz): 15.1,

30.9, 59.2, 70.5, 70.7, 71.7, 72.1, 94.8, 118.0, 118.2, 124.1, 124.3, 126.4, 129.0, 129.7, 130.7,

133.6, 134.9, 135.6, 138.3, 139.8, 140.7, 141.5, 141.9, 152.2. EI-MS, m/z (%): 1094.1 ([M],

100). Anal. Calcd for C51H54BF2IN2O6S4 (Mr = 1094.96): C, 55.94; H, 4.97; N, 2.56; Found:

C, 55.78; H, 4.62; N, 2.40.

S10

3) NMR spectra.

Figure S1: NMR spectrum 1H of compound 1 in CDCl3.

S11

Figure S2: NMR spectrum 13C of compound 2 in CDCl3.

S12

Figure S3: NMR spectrum 1H of compound TB1 in CDCl3.

S13

Figure S4: NMR spectrum 13C of compound TB1 in CDCl3.

S14


S15


S16


S17


S18


S19


S20


S21

Figure S12: NMR spectrum 1H of compound 7 in (CD3)2CO.

S22

Figure S13: NMR spectrum 13C of compound 7 in (CD3)2CO.

S23


S24


S25


S26


S27


S28

Figure S19: NMR spectrum 1H of compound 10 in (CD3)2CO.

S29


S30


S31


S32


S33


S34


S35


S36


S37


S38


S39

4) DSC traces for TB n.

DSC. Differential scanning calorimetry analyses were performed on a DSC Q200 apparatus

from TA Instruments. The analyses were carried out under nitrogen at a heating rate of

10°C.min-1.

Figure S30: DSC thermogram for TB1 obtained at a rate of 10°C/min.


S40



S41

5) X-ray crystallographic data for TB 2.

Single crystal of TB2 was mounted in oil on a nylon loop and placed in the nitrogen cold

stream (193 K) of a Rigaku mm007 HF diffractometer equipped with a Rapid II curved

Image-Plate detector and a CuKα rotating anode source with Osmic confocal CMF optics. A

total of 159 images with 5° rotation per image and 60 second exposure per degree of

oscillation were measured according to a ω-scan profile data strategy derived by the

CrystalClear software package.9 Intensities were reduced and merged after empirical

absorption correction using Fs_process within CrystalClear. Resolution limit was set upon

I/σ(I) to 2θ = 108° (0.95 Å). The structure was solved by direct methods (SHELXS-97)10 and

refined on F2 by means of full-matrix least-squares methods (SHELXL-97)10. All non-

hydrogen atoms were refined anisotropically whereas hydrogen atoms were placed at the

calculated positions and refined using a riding model. ORTEP drawings were made using

ORTEP311 as implemented within PLATON12 and packing studies were carried out using

MERCURY.13 See supporting CIF file for further refinement details.

Results for compound TB2: C49 H50 B F2 I N2 S4, Mr= 970.86, dark squared thick plate, 0.26 x

0.25 x 0.07 mm, triclinic, space group P -1 (n° 2), a= 12.0762(8) Å, b= 13.2664(8) Å, c=

15.0653(11) Å, α= 80.999(6) °, β= 71.602(5) °, γ= 83.461(6) °, V= 2256.6(3) Å3, Z=2, ρcalcd=

1.429 g.cm-3, 2θmax = 107.98 °, 19611 measured reflections, 5424 independent, -12 ≤ h ≤ 12, -

12 ≤ k ≤ 13, -15 ≤ l ≤ 15, R(int) = 0.0768, µ= 7.658 mm-1, multi-scan absorption correction,

relative Tmin= 0.385 and Tmax= 1.000, 536 parameters were refined against all reflections, 6

anisotropic parameters restraints were used, R1= 0.094, wR2= 0.1658 (using all data) based

on observed F values, R1= 0.061, wR2= 0.1327 (3376 reflections with I>2σ(I)), ∆ρmin and

ρmax = -0.862 and 0.649 e.Å-3, GOF=1.115 based on F2.

6) Atomic Force Microscopy investigations.

The thin film morphology was investigated by tapping mode atomic force microscopy on the

Nanoscope IV system commercialized by Veeco®.

The investigated substrates, thin films composition and annealing conditions were identical to

those that lead to the optimized performances from solution chloroform, reported in table 1.

These are:

i) TB1:PCBM (1:2), 70°, 20 min, figure S34a

ii) TB2:PCBM (1:0.5), 120°, 20 min, figure S34b

iii) TB3:PCBM (1:2), without annealing, figure S34c

iv) TB4:PCBM (1:1), 80°C, 20 min, figure S34d

S42

Figure S34: Surface topography obtained by tapping mode AFM. (a) TB1:PCBM(1:2) after

70°C, 20 min; (b) TB2:PCBM(1:0.5) after 120°C 20 min; (c) TB3:PCBM(1:2); (d) TB4:PCBM

(1:1) after 80° 20min.

S34a

S34b

S43

S34c

S34d

S44

7) Absorption and Fluorescence Spectra

Table S1. Selected spectroscopic data for the novel dyes.

Dye λabs

(nm) ε (M-1.cm-1)

λem (nm)

Φf @ λexc

nma) τ

(ns)

kr b)

(107 s-1)

knrb)

(107 s-1)

solvent

TB1 667 146000 683 78%

@600nm 3.3 23.6 6.6 THF

TB2 714 104000 743 7.5%

@620nm 0.87 8.6 106 THF

TB3 724 97200 763 2.7%

@680nm 0.68 4 143 THF

TB4 713 98000 749 6.5%

@630nm 0.85 7.6 110 THF

a) Using Rhodamine 6G as reference, λex = 488 nm, Φ= 0.78 in water for TB1,14 and

tetramethoxydiisoindomethene-difluoroborate (φF = 0.51 in methanol) for the others.15

b) Calculated using the following equations : kr = ΦF /τF, knr = (1-ΦF)/ τF, assuming that the

emitting state is produced with unit quantum efficiency.

S45

Figure S35. Absorption (dark line), emission (λexc = 512 nm red line) and excitation (λemi =

680 nm green line) spectra of TB1 (c = 3 x 10-6 M in THF).

Figure S36. Absorption in thin film (red line) and solution in THF (blue line) of TB1.

S46

Figure S37. Absorption (dark line), emission (λexc = 680 nm red line) and excitation (λem =

800 nm green line) spectra of TB3 (c = 3 x 10-6 M in THF).


S47

Figure S39. Absorption (blue line), emission (λexc = 630 nm red line) and excitation (λem =

780 nm purple line) spectra of TB4 (c = 3 x 10-6 M in THF).


S48

8) Cyclic voltammetry traces and Data

Table S2. Selected electrochemical data for the novel dyes.

Compd ∆∆∆∆Eopt

eV

E1/2ox

V

E1/2red

V

ΕΕΕΕHOMO

eV

ΕΕΕΕLUMO

eV

∆∆∆∆E

eV

TB1 1.60 0.68 (62mV)

1.06 (80mV)

-0.97 (60mV)

-1.87 (irr) -5.46 -3.81 1.65

TB2 1.45

0.64 (64 mV)

0.82 (65mV)

1.47 (76mV)

-0.89 (61mV)

-1.62 (irr) -5.32 -3.86 1.46

TB3 1.42

0.57 (68mV)

0.65 (64mV)

1.2 (81mV)

-0.94 (69mV) -5.30 -3.85 1.45

TB4 1.48 0.63 (64mV)

0.82 (65mV)

-0.93 (64mV)

-5.34 -3.84 1.50

Figure S41. Cyclic voltamogramm of compound TB3 in dichloromethane at rt. 1.5 mM

substrate in 0.10 M Bu4NPF6.

Figure S42. Cyclic voltamogram of compound TB4 in dichloromethane at rt. 1.5 mM

substrate in 0.10 M Bu4NPF6.

S49

9) Device preparation and characterization

Field Effect Transistors elaboration.

Bottom contact field-effect transistors (FETs) were elaborated on commercially available

pre-patterned test structures whose source and drain contacts were composed of a 30 nm thick

gold layer on top of a 10 nm thick Indium Tin Oxide (ITO) layer. A 230 nm thick silicon

oxide was used as gate dielectric and n-doped (3x1017 /cm3) silicon crystal as gate electrode.

The channel length and channel width were 20 µm and 10 mm, respectively. The test

structures were cleaned in acetone and isopropyl alcohol and subsequently for 15 minutes in

an ultra-violet ozone system. Then, hexamethyldisilazane (HMDS) was spin coated (500 rpm

for 5 s and then 4000 rpm for 50 s) under nitrogen ambient and followed by an annealing step

at 130°C for 5 minutes. Finally, 4 mg/ml anhydrous chloroform TBn or TB2:PC61BM

solutions were spin coated (2200 rpm for 180s and 2500 rpm for 120s) to complete the FET

devices. The samples were then left overnight under vacuum (<10-6 mbar) to remove residual

solvent traces. Both, the FET elaboration and characterizations were performed in nitrogen

ambient. The transistor output and transfer characteristics were recorded using a Keithley

4200 semiconductor characterization system. The charge carrier mobility was extracted in the

saturation regime using the usual formalism.

S50

Table S3. Measured charge carrier mobility in the different dyes.

Dye µh (cm2/Vs) µe (cm2/Vs) TB1 1x10-4 / TB2 1x10-3 1x10-3 TB3 1x10-8 / TB4 6x10-7 /

Figure S43. Charge carrier mobilities calculated from FET’s transfer characteristics using

different TB2:PC61BM weight ratio.

1.E-07

1.E-06

1.E-05

1.E-04

1.E-03

1.E-02

1.E-01

0 1 2 3 4 5

Mo

bilit

y (c

m2 /

V.s)

TB:PC61BM wt. ratio

holes

electrons

1:0 1:0.8 1:4 0:1

10-1

10-2

10-3

10-4

10-5

10-6

10-7

Photovoltaic devices elaboration and characterization.

Bulk heterojunction devices were elaborated using the different synthesized molecules as

electron donor and PC61BM as electron acceptor. The standard device structure was the

following: ITO/PEDOT:PSS(~40 nm)/TBn:PC61BM/Al(~120 nm). Indium Tin Oxide coated

glass with a surface resistance lower than 20 Ω/sq was used as transparent substrate.

Substrates were cleaned sequentially by ultrasonic treatments in acetone, isopropyl alcohol,

and deionized water. After an additional cleaning for 30 minutes under ultra-violet generated

ozone, a highly conductive polyethylene dioxythiophene: polystyrene-sulphonate

PEDOT:PSS was spin coated (1500 rpm: 40 nm) from an aqueous solution and dried for 30

minutes at 120°C under vacuum before being transferred to the nitrogen filled glove box. The

S51

chloroform, chlorobenzene or chloroform/chlorobenzene molecule:PC61BM solutions were

stirred for at least 24 hours at 50°C before spin-coating. An extra stirring for 30 minutes at

100°C was added just before the active layer deposition. The molecule concentration of the

solution was varied from 5 mg/ml for chloroform solutions up to 40 mg/ml for chlorobenzene

solutions in order to obtain different active layer thicknesses and morphologies. The relative

TBn:PC61BM weight ratio was also varied from 1:0.2 to 1:3. The active layer spin coating

conditions were the same for all solvents: a first 180 seconds step (speed: 2200 rpm,

acceleration: 600 rpm/s) followed by a second 120 seconds step (speed: 2500 rpm,

acceleration: 600 rpm/s). Finally, a 120 nm thick aluminum layer was thermally evaporated

and used as cathode. The device active area was 9 mm2, while each sample included four

independent diodes. With the most promising molecule, an extra series of devices was

elaborated with and an additional Ca (20 nm) layer between the active layer and the

aluminum cathode. Current versus Voltage (J-V) characteristics were measured using a source

measurement unit Keithley 2400 under darkness and under AM1.5G (100 mW/cm2)

illumination. The standard illumination was provided by an Oriel 150 W (filtered Xe lamp)

solar simulator and the illumination power was calibrated using a THORLABS optical power

meter. External Quantum Efficiency (EQE) measurements were performed using a focused

light beam (on a standard silicon reference cell or on the solar cell under study) from a 250 W

halogen lamp passing through a filter wheel. The photovoltaic cells elaboration after substrate

preparation and the characterizations were performed in nitrogen ambient except the EQE

measurements.

S52

Table S4. Survey of the different experimental conditions tested for the photovoltaic devices

and the corresponding measurements (the results with a bold frame are included in the main

text). Dye TBn:PCBM

ratio Acceptor Voc (V) Jsc

(mA/cm2) FF (%)

PCE (%) Annealing Solvent Concentration

(Dye/ml)

d (nm)

TB1 1:0.8 PC61BM 0.73 3.6 27 0.7 70°C, 10m CHCl3 5mg/ml 110±10

TB1 1:1 PC61BM 0.68 3.4 28 0.6 70°C, 10m CHCl3 5mg/ml 110±10

TB1 1:2 PC61BM 0.76 5.8 31 1.4 70°C, 20m CHCl3 5mg/ml 110±10

TB1 1:3 PC61BM 0.74 4.9 32 1.2 70°C, 10m CHCl3/CB (1/1) 5mg/ml

TB1 1:2 PC61BM 0.74 4.5 31 1.0 70°C, 10m CB 10mg/ml



TB2 1:2 PC61BM 0.65 5.4 29 1.0 - CHCl3/CB (1/1) 8mg/ml

TB2 1:0.8 PC61BM 0.72 11.9 49 4.3 100°C, 10m CB 20mg/ml

TB2 1:0.8 PC61BM 0.74 14.3 42 4.5 100°C, 10m CB 40mg/ml 165±10

*TB 2 1:0.2 PC61BM 0.77 11.4 41 3.6 100°C, 10m CB 40mg/ml 165±10

*TB 2 1:0.5 PC61BM 0.70 14.3 47 4.7 100°C, 10m CB 40mg/ml 165±10

*TB 2 1:0.8 PC61BM 0.59 10.9 42 2.7 100°C, 10m CB 20mg/ml

*TB 2 1:0.2 PC71BM 0.73 9.3 39 2.7 100°C, 10m CB 40mg/ml 165±10

TB3 1:2 PC61BM 0.56 5.1 30 0.9 - CHCl3 5mg/ml 110±10

TB3 1:0.8 PC61BM 0.51 4.1 31 0.6 80°C, 10m CB 20mg/ml

TB3 1:1 PC61BM 0.50 4.7 32 0.7 80°C, 10m CB 20mg/ml

TB3 1:0.8 PC61BM 0.50 3.0 31 0.5 80°C, 10m CB 40mg/ml 165±10

TB3 1:1 PC61BM 0.51 3.3 33 0.6 80°C, 10m CB 40mg/ml 165±10

TB4 1:1 PC61BM 0.55 8.5 32 1.5 80°C, 20 m CHCl3 5mg/ml 110±10

TB4 1:1 PC61BM 0.48 6.1 30 0.9 80°C, 20 m CHCl3/CB (1/1) 5mg/ml

TB4 1:0.8 PC61BM 0.51 5.0 30 0.8 - CB 20mg/ml

TB4 1:0.8 PC61BM 0.57 2.3 30 0.4 - CB 40mg/ml 165±10

*Ca(20 nm)/Al(120 nm) cathode and annealing before cathode deposition

S53

10) Additional References

1 Lipset, F. R. Prog. Dielectr. 1967, 7, 217. 2 Olmsted, J. III, J. Phys. Chem. 1979, 83, 2581 3 S. Pu and al., J. Mol. Struc. 2009, 921, 89-100. 4 N. Leclerc and al. Chem. Mater., 2005, 17, 502-513. 5 T. Bura, R. Ziessel Org.Lett. 2011, 13, 3072-3075. 6 P. Frère and al. J. Org. Chem., 2003, 68, 7254-7265. 7 Rousseau, T.; Cravino, A.; Bura, T.; Ulrich, G.; Ziessel, R.; Roncali, J. Chem. Commun.

2009, 1673-1675. 8 Hou. Q. and al. J. Mater. Chem. 2002, 12, 2887-2892. 9 CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009). 10 Sheldrick, G.M. (2008). Acta Cryst. A64, 112-122; Welter, R. Acta Cryst. 2006, A62,

s252.. 11 ) Burnett, Michael N. and Johnson, Carroll K.(1996). ORTEP-III: Oak Ridge Thermal

Ellipsoid Plot Program for Crystal Structure Illustrations, Oak Ridge National

Laboratory Report ORNL-6895. 12 Spek, A. L. J. Appl. Cryst. 2003, 36, 7-13. 13 Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R.,

Towler, M. & van de Streek, J. J.Appl. Cryst. 2006, 39, 453-457. 14 Olmsted III, J. J. Phys. Chem. 1979, 83, 2581-2584. 15 Ulrich, G. ; Goeb, S. ; De Nicola, A. ; Retailleau, P. ; Ziessel R. Synlett. 2007, 1517-1520.

Documents

Supporting Information (53 pages) Table of Contents Pages fileHeiser, 3 Pascal Retailleau, 4 Sandra Rihn, 1 Antoine Mirloup, 1 and Raymond Ziessel 1 Supporting Information (53 pages)