Supporting Information

 Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2012

Tripyridyltruxenes: Thermally Stable Cathode Buffer Materials for Organic Thin-Film Solar Cells
Hayato Tsuji,*[a, b] Yoshinori Ota,[a] Shunsuke Furukawa,[a] Chikahiko Mitsui,[a] Yoshiharu Sato,[c] and Eiichi Nakamura*[a, c]
ajoc_201200021_sm_miscellaneous_information.pdf

Experimental Section General. All reactions dealing with air- or moisture-sensitive compounds were Analytical thin-layer

carried out in dry reaction vessel under nitrogen.

chromatography was performed on glass plates coated with 0.25 mm 230400 mesh silica gel containing a fluorescent indicator (Merck). Flash silica gel column

chromatography was performed on silica gel 60N (Kanto, spherical and neutral, 140 325 mesh) as described by Still. 1 Gel permeation column chromatography was

performed on a Japan Analytical Industry LC-908 (eluent: chloroform) with JAIGEL 1H and 2H polystyrene columns. Melting points were uncorrected. NMR spectra

were measured on JEOL ECX-400 and ECA-500 and reported in parts per million from tetramethylsilane. Routine mass spectra were acquired by Shimadzu GC-2010

(GC-MS) and APCI using a time-of-flight mass analyzer on JEOL JMS-T100LC (AccuTOF) spectrometer with a calibration standard of polyethylene glycol (MW ~ 1000).

Materials. 1-Indanone

Unless otherwise noted, commercial reagents were used as purchased. was purchased from Tokyo Kasei Co.

Tetrakis(triphenylphosphine)palladium(0) was prepared according to a literature. 2 Truxene was prepared according to the reported procedure.3 Instruments. Mass spectra were taken at JEOL Accu TOF JMS-T100LC. Melting points of solid materials were determined on a Mel-Temp II capillary melting-point apparatus and uncorrected. High vacuum (pressure under 30 mTorr) train sublimation

was performed with P-100HT (ALS Technology Co. Ltd.).

1. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 29232925. 2. (a) Saroja, G.; Pingzhu, Z.; Ernsting, P. N.; Liebscher, J. J. Org. Chem. 2004, 69, 987990. (b) Dehmlow, V. E.; Kelle, T. Synth. Commun. 1997, 27, 20212030. (c) Yuan, M.-S.; Fang, Q.; Liu, Z.-Q.; Guo, J.-P.; Chen, H.-Y.; Yu, W.-T.; Xue, G.; Liu, D.-S. J. Org. Chem. 2006, 71, 78587861. 3. Dehmlow, V. E.; Kelle, T. Synth. Commun. 1997, 27, 20212030. S1

Nuclear magnetic resonance spectroscopy (NMR).

Proton nuclear magnetic

resonance (1H NMR) and carbon nuclear magnetic resonance (13C NMR) spectra were recorded with JEOL ECA-500 (500 MHz) NMR spectrometer. Chemical data for

protons are reported in parts per million (ppm, scale) downfield from tetramethylsilane ( 0.00). Carbon nuclear magnetic resonance spectra (13C NMR)

were recorded at 125 MHz: chemical data for carbons are reported in parts per million (ppm, scale) referenced to the carbon resonance of the NMR solvent (CDCl3: 77.0). The data are presented as follows: chemical shift, multiplicity (s = single, d = doublet, t = triplet, m = multiplet and/or multiplet resonance) coupling constant in Hertz (Hz), and integration.

Synthesis
Br t-BuOK (20 eq) MeI (20 eq) DMSO 0 C to r.t., 20 h Br2 (3.5 eq) Br CH2Cl2 r.t., 8 h

1 88%

Br 2 92%

5,5,10,10,15,15-Hexamethyltruxene (1).

Truxene (5.00 g, 14.6 mmol), dimethyl

sulfoxide (60 mL), and potassium tert-butoxide (10.11 g, 90.5 mmol) were placed into a 3-neck 300-mL flask, and the mixture was cooled to 0 C. To the mixture, methyl

iodide (12.50 g, 5.48 mL, 88.1 mmol) was added dropwise and the resulting mixture was allowed to warm to room temperature and stirred. After 30 min, additional

potassium tert-butoxide (5.03 g, 44.8 mmol) and methyl iodide (12.68 g, 89.3 mmol) were added in the same manner. After 14 h, additional potassium tert-butoxide (15.07

g, 134 mmol) and methyl iodide (12.39 g, 87.3 mmol) were added in the same manner and stirred for total 18 h. Water (300 mL) and ethyl acetate (100 mL) were added to The organic layer was extracted by ethyl acetate

the mixture to quench the reaction.

(100 mL 3) and the combined organic layer was washed with brine (100 mL) and dried over magnesium sulfate. After filtration, the volatile was evaporated. Because

the methylation was not completed, to the obtained product in a 2-neck 200-mL flask, S2

dimethylsulfoxide (60 mL), and potassium tert-butoxide (4.98 g, 44.3 mmol) were added. Then, methyl iodide (6.24 g, 44.0 mmol) was added dropwise at 0 C and the After that, water

mixture was allowed to attain room temperature and stirred for 3 h.

(50 mL) and ethyl acetate (50 mL) were added to the mixture. The organic layer was extracted by ethyl acetate (200 mL 3) and the combined organic layer was washed with brine (100 mL) and dried over magnesium sulfate. was evaporated in vacuo. After filtration, the solvent from hot

Recrystallization

1,1,2,2-tetrachloroethane/methanol gave 1 in 88% (5.48 g, gray powder).

Mp: 304

305 C. 1H NMR (500 MHz, CDCl3) 1.89 (s, 18H), 7.387.44 (m, 6H), 7.55 (d, J = 6.9 Hz, 3H), 8.31 (d, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) 24.0, 46.8, 122.5, 125.6, 126.2, 126.8, 135.7, 136.7, 148.3, 157.5; GC-MS (EI) 426 (M+ for C33H30). Anal. Calcd for C33H30: C, 92.91; H, 7.09. Found: C, 92.71; H, 7.16.

3,8,13-Tribromo-5,5,10,10,15,15-hexamethyltruxene (2).

The hexamethyltruxene 1

(5.48 g, 12.8 mmol) in dichloromethane (270 mL) was placed into a 3-neck 500-mL flask. To the solution, bromine (7.17 g, 2.30 mL, 44.9 mmol) was added and the To the reaction mixture, saturated The organic layer was

mixture was stirred at room temperature for 7.5 h.

aqueous solution of sodium thiocarbonate (200 mL) was added.

extracted by dichloromethane (100 mL 2) and the combined organic layer was washed with brine (100 mL) and dried over magnesium sulfate. solvent was evaporated in vacuo. After filtration, the from hot

Recrystallization

1,1,2,2-tetrachloroethane/methanol gave 2 in 92% (7.79 g, gray powder).

Mp: 347

348 C. 1H NMR (500 MHz, CDCl3) 1.83 (s, 18H), 7.54 (dd, J = 1.7, 8.6 Hz, 3H), 7.65 (d, J = 1.7 Hz, 3H), 8.10 (d, J = 8.6 Hz, 3H); 13C NMR (125 MHz, CDCl3) 23.8, 47.1, 121.2, 126.0, 126.9, 129.6, 135.0, 135.3, 148.2, 159.4; LCMS(APCI+) 664.05 [M+1]. Anal. Calcd for C33H27Br3: C, 59.76; H, 4.10. Found: C, 59.63; H, 4.18.

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3,8,13-Triphenyl-5,5,10,10,15,15-hexamethyltruxene (PhTx)
Br Br +

B(OH)2 (6.0 eq)

Pd(PPh3)4 (5 mol%) THF/2M Na2CO3aq. 100 C, 14 h

Br 90%

The tribromide 2 (299 mg, 450 mol), phenylboronic acid (329 mg, 2.70 mmol), THF (6.1 mL), 2M aqueous solution of Na2CO3 (4.5 mL), and Pd(PPh3)4 (26.4 mg, 22.5 mol) were placed into a Schlenk tube, and the mixture was stirred for 14 h at 100 C. After heating, saturated aqueous solution of ammonium chloride (20 mL) was added, and the organic layer was extracted with AcOEt (20 mL 3). The combined organic

layer was washed with brine (100 mL), dried over magnesium sulfate, and filtrated. After the volatile of the filtrate was evaporated, the crude product was passed through a pad of silica short gel. Reprecipitation from hot 1,1,2,2-tetrachloroethane/methanol Mp: 360361 C. 1H NMR (500 MHz,

gave PhTx in 90% (264 mg, white powder).

CDCl3) 1.98 (s, 18H), 7.40 (brt, J = 7. 5 Hz, 3H), 7.52 (dd, J = 7.5, 8.0 Hz, 6H), 7.69 (dd, J = 1.8, 8.0 Hz, 3H), 7.75 (brs, 3H), 7.77 (dd, J = 1.8, 8.0 Hz, 6H), 8.38 (d, J = 8.0 Hz, 3H); 13C NMR (125 MHz, CDCl3) 24.2, 47.0, 121.1, 125.4, 125.9, 127.2, 127.3, 128.8, 135.4, 136.0, 139.7, 141.2, 148.5, 158.2; LCMS (APCI+) 655.40 [M+1]. Anal. Calcd for C51H42: C, 93.54; H, 6.46. Found: C, 93.48; H, 6.53. 3,8,13-Tri(2-pyridyl)-5,5,10,10,15,15-hexamethyltruxene
N Br Br + N ZnBr

Pd(PPh3)4 (15 mol%) THF, 90 C, 17 h

(3.7 eq) 2 Br 88% N

The tribromide 2 (30 mg, 45 mol), 2-pyridylzinc bromide in hexane (0.5 M, 335 L, S4

167 mol), THF (1.68 mL), and Pd(PPh3)4 (7.8 mg, 6.8 mol) were placed into a Schlenk tube and the mixture was stirred for 17 h at 90 C. After heating, water (5 The

mL) was added, and the organic layer was extracted with CH2Cl2 (10 mL 3).

combined organic layer was washed with brine (10 mL), dried over magnesium sulfate, and filtrated. After the solvent of the filtrate was evaporated. Flash silica gel column

chromatography (20% to 100% AcOEt in hexane) gave 2PyTx (Rf = 0.59, AcOEt) in 88% (25.9 mg, pale yellow solid). Mp: 361362 C. 1H NMR (500 MHz, CDCl3)

2.01 (s, 18H), 7.277.29 (m, 3H), 7.82 (ddd, J = 1.7, 7.5, 8.0 Hz, 3H), 7.89 (d, J = 8.0 Hz, 3H), 8.06 (dd, J = 1.7, 8.0 Hz, 3H), 8.25 (d, J = 1.7 Hz, 3H), 8.43 (d, J = 8.0 Hz, 3H), 8.78 (brd, J = 4.0 Hz, 3H); 13C NMR (125 MHz, CDCl3) 24.1, 47.1, 120.6, 120.9, 122.0, 125.2, 125.9, 135.4, 136.8, 137.5, 137.9, 149.3, 149.8, 157.4, 158.2; LCMS (APCI+) 658.41 [M+1]. Anal. Calcd for C48H39N3: C, 87.64; H, 5.98; N, 6.39. Found: C, 87.55; H, 6.17; N, 6.29.

3,8,13-Tri(3-pyridyl)-5,5,10,10,15,15-hexamethyltruxene (3PyTx)
N Br Br + N (6.0 eq) 2 Br N 97%

B(OH)2 Pd(PPh ) (5 mol%) 3 4 THF/2M Na2CO3aq. 100 C, 6.5 h

The tribromide 2 (591 mg, 891 mol), 3-pyridineboronic acid (657 mg, 5.34 mmol), THF (12.0 mL), 2M aqueous solution of Na2CO3 (9.0 mL), and Pd(PPh3)4 (51.5 mg, 44.6 mol) were added into a Schlenk tube and the mixture was stirred for 6.5 h at 100 C. After heating, saturated aqueous solution of ammonium chloride (40 mL) was added, and the organic layer was extracted with CH2Cl2 (50 mL 3). The combined

organic layer was washed with brine (100 mL), dried over magnesium sulfate, and filtrated. After the volatile of the filtrate was evaporated, the crude product was passed Reprecipitation from hot 1,1,2,2-tetrachloroethane/hexane S5

through a pad of silica gel.

gave 3PyTx in 97% (568 mg, white powder).

Mp: 359360 C. 1H NMR (500 MHz,

CDCl3) 1.99 (s, 18H), 7.45 (dd, J = 4.6, 8.0 Hz, 3H), 7.70 (dd, J = 1.7, 8.0 Hz, 3H), 7.78 (d, J = 1.7 Hz, 3H), 8.04 (brd, J = 8.0 Hz, 3H), 8.43 (d, J = 8.0 Hz, 3H), 8.65 (brd, J = 4.6 Hz, 3H), 9.01 (d, J = 1.7 Hz, 3H); 13C NMR (125 MHz, CDCl3) 24.1, 47.1, 121.1, 123.6, 125.5, 126.2, 134.3, 135.3, 136.4, 136.61, 136.63, 148.4, 148.5, 149.0, 158.4; LCMS (APCI+) 658.38 [M+1]. Anal. Calcd for C48H39N3: C, 87.64; H, 5.98; N, 6.39. Found: C, 87.56; H, 6.10; N, 6.20.

3,8,13-Tri(4-pyridyl)-5,5,10,10,15,15-hexamethyltruxene (4PyTx)
N Br Br + N (6.0 eq) 2 Br 64% N N

B(OH)2 Pd(PPh ) (5 mol%) 3 4 THF/2M Na2CO3aq. 100 C, 41.5 h

The tribromide 2 (359 mg, 540 mol), 4-pyridineboronic acid (399 mg, 3.24 mmol), THF (7.3 mL), 2 M aqueous solution of Na2CO3 (5.4 mL), and Pd(PPh3)4 (31.2 mg, 27.0 mol) were added into a Schlenk tube and the mixture was stirred for 41.5 h at 100 C. After heating, saturated aqueous solution of ammonium chloride (40 mL) was added and the solvent was evaporated. The residue was triturated with CH2Cl2 and the solid

was dissolved in hot 1,1,2,2-tetrachloroethane and the insoluble material was removed by filtration. After the volatile of the filtrate was evaporated, the residue was Reprecipitation

subjected to flash silica column chromatography (Rf = 0.16, acetone).

from hot 1,1,2,2-tetrachloroethane/acetone and methanol gave 4PyTx in 64% (228 mg, pale yellow powder). Mp: 411412 C. 1H NMR (500 MHz, CDCl3) 1.99 (s, 18H),

7.66 (d, J = 5.8 Hz, 6H), 7.77 (dd, J = 1.8, 8.6 Hz, 3H), 7.83 (d, J = 1.8 Hz, 3H), 8.43 (d, J = 8.6 Hz, 3H), 8.74 (d, J = 5.8 Hz, 6H); 13C NMR (125 MHz, CDCl3) 24.1, 47.1, 121.0, 121.6, 125.5, 126.2, 135.2, 136.7, 137.5, 148.2, 149.4, 150.3, 158.3; LCMS (APCI+) 658.38 [M+1]. Anal. Calcd for C48H39N3: C, 87.64; H, 5.98; N, 6.39. Found: C, 87.32; H, 6.05; N, 6.18. S6

Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) CV and DPV were performed using HOKUTO DENKO HZ-5000 voltammetric analyzer. All measurements were carried out in a one-component cell under Ar gas,

equipped with a glassy-carbon working electrode, a platinum counter-electrode, and an Ag/Ag+ reference electrode for a dichloromethane solution at a concentration of 0.5 mM. The supporting electrolyte was a 0.1-M solution of tetrabutyl ammonium hexafluorophosphate (TBAPF). All potentials were corrected against Fc/Fc+. CV

was measured with a scan rate of 100 mV/s. The CV and DPV traces are shown in Figure S1 and summarized in Table S1.
CV PhTx CV 2PyTx

DPV

DPV

CV 3PyTx

CV 4PyTx

DPV

DPV

Figure S1. Cyclic voltammograms and differential pulse voltammograms of the Txs. Table S1. The first reduction potentials and estimated LUMO energy levels of the Txs Ered (V) ELUMO (eV) PhTx 2.87 1.93 2PyTx 2.70 2.10 3PyTx 2.77 2.03 4PyTx 2.57 2.23 S7

UVvis absorption spectroscopy UVvis absorption spectra were recorded with a JASCO V-570 spectrometer. All measurements were carried out for a dichloromethane solution at a concentration of 0.5 105 M or 1.0 105 M.

Figure S2. UVvis absorption spectra of the TXs measured in CH2Cl2 at room temperature. Table S2. Absorption properties and HOMOLUMO energy gaps max (nm)a PhTx 2PyTx 323 330 10-4 (cm-1M-1) 15.5 11.1 11.6 8.94

3PyTx 323 4PyTx 326 a Maximum absorption wavelength. S8

Thermogravimetry-differential thermal analysis (TG-DTA) Thermal properties of the materials were measured with Rigaku TG8120. Temperature was raised at 10 K/min under N2. Temperature difference from a reference sample (Al2O3) and relative weights were measured as a function of temperature as shown in Figure S3. The decomposition temperatures (Td), at which 5% of the weigh of the

sample was lost, show that PyTXs are thermally more stable than PhTX.

Figure S3. TG-DTA traces of TXs

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Fabrication of OPV devices On a clean glass substrate precoated with a 145-nm-thick ITO (indium tin oxide) layer with a sheet resistance of 8.4 W/sq, PEDOT:PSS dispersed in water was spin-coated at 3000 rpm for 30 sec under air. The substrate was pre-baked at 120 C for 10 min

under air for dryness. The substrate was placed in a nitrogen-purged glove box and heated at 180 C for 10 min. In the glove box, a BP (benzophorphyrine) layer was formed on the PEDOT:PSS layer by spin-coating (1,500 rpm) a precursor solution that contained 0.5 wt% of CP in a chloroform/chlorobenzene mixture (1:2) and following thermal conversion at 180 C for 20 min to transform to BP from CP. The thickness of

the crystallized BP p-layer was 25 nm. On top of the BP layer, the i-layer was deposited by spin coating (1,500 rpm) a mixture of CP and SIMEF-Ph,o-An (CP, 0.6 wt%; SIMEF-Ph,o-An, 0.8 wt%) in a chloroform/chlorobenzene mixture (1:1). The i-layer

was heated at 180 C for 20 min. After this thermal conversion, the n-layer, consisting of SIMEF-Ph,o-An (0.7 wt%) in toluene, was spin-coated (1,000 rpm) on the i-layer. After drying this layer at 120 C for 10 min, the cathode buffer materials were deposited with 5 nm thickness under vacuum (104 Pa) on the top layer, respectively. Then, the top electrode (Al, 80 nm) was deposited with a metal shadow mask, which defined a 2-mm stripe pattern perpendicular to the ITO stripe. Finally, the whole devices were annealed at 80 C for 10 min, then the cells were encapsulated with backing glasses using a UV-curable resin under nitrogen atmosphere.

Evaluation of J-V characteristics of OPV devices Current density-voltage curves were measured with Spectrum Radiation Equipment (Sumitomo Heavy Industries Advanced Machinery Co. Ltd.) under AM1.5G irradiation. All the measurements were carried out under an ambient atmosphere.

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Figure S4. J-V characteristics of the solar cells using the triaryltruxenes

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