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1 Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 206 Supporting information Synthesis of organic photosensitizers containing dithienogermole and thiadiazolo[3,4-c]pyridine units for dye-sensitized solar cells Yohei Adachi, a Yousuke Ooyama, a Naoyuki Shibayama b and Joji Ohshita* a a Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima , Japan. jo@hiroshima-u.ac.jp; Fax: ; Tel: b Technical Research Institute, Toppan Printing Co., Ltd, Takanodaiminami, Sugito, Saitama , Japan Contents Experimental General Control experiment , 3 Synthesis of donor unit , 5 Synthesis of acceptor unit , 7, 8 Absorption spectra (on TiO) Cyclic voltammograms EIS Nyquist plots H NMR spectra of DTG-containing dyes , References

2 Experimental General All reactions were carried out under dry argon. For the reaction solvents, THF, DMF, toluene, chloroform, dichloromethane were purchased from Kanto Chemical Co. Ltd. They were distilled from calcium hydride and stored over activated molecular sieves until use, while chloroform and dichloromethane were distilled from calcium hydride immediately before use. Usual workup mentioned below includes hydrolysis of the reaction mixture with water and separation of the organic layer. The aqueous layer was extracted with toluene, chloroform, hexane or ethyl acetate. The organic layer and the extract were combined and washed with water. After drying over anhydrous magnesium sulfate, the solvent was evaporated. Starting materials, DTGBr [S], 4- (trimethylstannyl)triphenylamine [S2], PTzBr2 [S3], 4-(thiophen-2-yl)-pyridine [S4], and 4,4,5,5- tetramethyl-2-[5-(4,4,5,5-tetramethyl-,3-dioxolan-2-yl)thiophen-2-yl]-,3,2-dioxaborolane (a-3) [S5] were prepared according to the literature methods. Control experiment A mixture of 52.6 mg (93.4 μmol) of DTS(2EH) or 60.3 mg (99.2 μmol) of DTG(2EH), 2.0 ml of M NaOH aq, and 2.0 ml of THF was heated at 50 o C for 2 h with stirring. After the mixture was cooled to room temperature, the usual workup gave the residue, which was characterized by H, C, 29 Si NMR and HR-mass spectrometry. Data for [5,5'-bis(trimethylsilyl)-3-(2,2'-bithienyl)]bis(2-ethylhexyl)silanol (diastereomeric mixture): H NMR (in CDCl 3): δ = 0.32 (8H, s, Me 3Si), (2H, m, CH 3), (20H, m, CH 2), 2

3 (2H, m, CH), 7.5 (H, d, J = 3.2 Hz, thiophene), 7.20 (H, d, J = 3.2 Hz, thiophene), 7.27 (H, s, thiophene). C NMR (in CDCl 3): δ = -0., -0., -0.0, -0.0, 0.6, 4., 22.0, 22.0, 22.0, 22., 22.9, 23.0, 28., 28.7, 28.8, 34.8, 34.8, 35.6, 35.6, 28.4, 42.5, 28.5, 28.5, 28.5, 28.6, 4.2, 4.2, 4.3, 4.3, 8.9, 8.9, 8.9, 40.7, 40.7, 40.7, 40.8, 40.8, 4.8, 42.6, 47.7, 47.7, Si NMR (in CDCl 3): δ = -6.9, -6.6, 5.9, 6.0, 6.. HR-MS (APCI) Calcd for C 30H 56OS 2Si 3: [M+H] + : , Found: No reaction took place for DTG(2EH). Figure S Full-scale H NMR spectra of DTG(2EH) and DTS(2EH) before and after hydrolysis. 3

4 Synthesis of donor unit Synthesis of 4-[4,4-Bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]germol-2-yl]phenyl-N,N-diphenylamine (d-) (diastereomeric mixture) A mixture of.48 mmol of 4-(trimethylstannyl)phenydiphenylamine, 803 mg (.48 mmol) of DTGBr, 27.8 mg (2.0 mol%) of Pd 2(dba) 3, 46.0 mg (0 mol%) of P(o-tol) 3, and 20 ml of toluene was heated at 00 ºC for.5 day with stirring. After usual workup using toluene for extraction, the residue was subjected to silica gel chromatography eluting with hexane/chloroform = /, then preparative GPC eluting with toluene to give 66 mg (0.935 mmol, 63% yield) of d- as a yellow oil: H NMR (in CD 2Cl 2): δ = (2H, m, CH 3), (20H, m, CH 2), (2H, m, CH), (4H, m, p-ph and phenylene), (5H, m, DTG and o-ph), 7.27 (H, d, J = 4.4 Hz, DTG), 7.29 (H, s, DTG), (4H, m, m-ph),7.53 (2H, d, J = 8.4 Hz, phenylene). C NMR (in CD 2Cl 2): δ =.2, 4.4, 2., 23.5, 29.6, 29.8, 29.40, 29.42, 35.9, 35.94, 37.5, 23.5, 24.3, 24.9, 25.3, 25.6, 26.7, 29.4, 29.8, 0.4, 43.86, 43.95, 44.04, 44.85, 44.87, 44.89, 45.20, 45.22, 45.23, 45.96, 46.04, 46., 46.83, 46.86, 46.89, 47.4, HR-MS (APCI) Calcd for C 42H 5GeNS 2: [M+H] + : , Found: Synthesis of 4-[4,4-Bis(2-ethylhexyl)-6-bromodithieno[3,2-b:2',3'-d]germol-2-yl]phenyl-N,Ndiphenylamine (d-2) (diastereomeric mixture) To a solution of 67 mg (0.237 mmol) of d- in 0 ml of dichloromethane was added 42.2 mg (0.237 mmol) of NBS in several portions and the mixture was stirred at room temperature for h with stirring. 4

5 After usual workup using chloroform for extraction, the residue was subjected to preparative GPC eluting with toluene to give 48 mg (0.88 mmol, 79% yield) of d-2 as a yellow oil: H NMR (in CD 2Cl 2): δ = (2H, m, CH 3), (20H, m, CH 2), (2H, m, CH), (5H, m), 7. (4H, dd, J = 8.8,.2 Hz, o-ph), 7.27 (H, s, DTG), (4H, m, m-ph), 7.48 (2H, d, J = 8.4 Hz, phenylene). C NMR (in CD 2Cl 2): δ =.,., 4.4, 2., 2.4, 23.4, 23.5, 29.6, 29.9, 29.3, 29.4, 35.85, 35.88, 37.4, 37.43, 0.66, 0.67, 0.69, 23.6, 24., 24.9, 25.5, 26.7, 29.0, 29.7, 3., 44., 44.2, 44.27, 44.34, 44.36, 44.39, 45., 45.2, 45.3, 45.42, 45.44, 45.46, 47.42, 47.44, 47.46, 47.53, HR-MS (APCI) Calcd for C 42H 50BrGeNS 2: M +. : , Found: Synthesis of 4-[4,4-Bis(2-ethylhexyl)-6-(trimethylstannyl)dithieno[3,2-b:2',3'-d]germol-2-yl]phenyl- N,N-diphenylamine (DTGSn) (diastereomeric mixture) To a solution of 682 mg (0.868 mmol) of d-2 in 20 ml of THF was added 0.70 ml (. mmol) of a solution of.58 M n-butyllithium in hexane at -78 ºC over a period of 30 min and the mixture was stirred at this temperature for 30 min with stirring. To this was added 226 mg (. mmol) of trimethyltin chloride at this temperature and the mixture was stirred at room temperature overnight. After usual workup using hexane for extraction, the residue was subjected to preparative GPC eluting with toluene to give 339 mg (0.390 mmol, 45% yield) as a yellow oil: H NMR (in CD 2Cl 2): δ = 0.42 (9H, s, Me 3Sn), (2H, m, CH 3), (20H, m, CH 2), (2H, m, CH), (4H, m, p-ph and phenylene), 7.4 (4H, dd, J = 8.4,.2 Hz, o-ph), 7.8 (H, s, DTG), 7.26 (H, s, DTG), (4H, m, m-ph), 7.5 (2H, d, J = 8.8 Hz, phenylene). C NMR (in CD 2Cl 2): δ = -8.0,.8,.22, 4.5, 2., 2.2, 23.5, 23.52, 29.3, 29.4, 29.5, 35.9, 36.0, 37.5, 37.6, 23.5, 24.3, 24.9, 25.8, 26.7, 29.6, 29.8, 8.4, 44.68, 44.70, 44.72, 45.37, 45.40, 45.43, 45.45, 45.5, 45.9, 46.0, 46.2, 47.4, 48., HR-MS (APCI) Calcd for C 45H 59GeNS 2Sn: [M+H] + : , Found:

6 Synthesis of acceptor unit Synthesis of 4-[5-(Trimethylstannyl)-2-thienyl]pyridine (a-) To a solution of 324 mg (2.0 mmol) of 4-(2-thienyl)pyridine in 0 ml of THF was added.8 ml (2.03 mmol) of a solution of. M LDA in hexane/thf at -78 ºC over a period of 0 min and the mixture was stirred at this temperature for h. To this was added 422 mg (2.2 mmol) of trimethyltin chloride at this temperature and the mixture was stirred at 35 ºC for 30 min. After usual workup using ethyl acetate for extraction, 634 mg (.96 mmol, 98% yield) of a- was obtained as a light brown solid. The crude product was analyzed by H, C NMR and MS spectrometry used for the following reaction without further purification: H NMR (in CDCl 3): δ = 0.4 (9H, s, Me 3Sn), 7.2 (H, d, J = 3.2 Hz, thiophene), (2H, m, pyridyl), 7.59 (H, d, J = 3.2 Hz, thiophene), (2H, m, pyridyl). C NMR (in CDCl 3): δ = -8.2, 9.9, 26.4, 6.4, 4.2, 4.3, 46.7, HR-MS (APCI) Calcd for C 2H 5NSSn: [M+H] + : , Found: Synthesis of 7-Bromo-4-[5-(4-pyridiyl)-2-thienyl][,2,5]thiadiazolo[3,4-c]pyridine (PTzPy) A mixture of 283 mg (0.959 mmol) of PTzBr2, 320 mg (0.988 mmol) of a-, 85 mg (5 mol%) of 6

7 Pd(PPh 3) 4, and 0 ml of DMF was heated at 20 ºC for h. After usual workup using chloroform for extraction, the residue was purified by preparative GPC eluting with chloroform to give 80.2 mg (0.24 mmol, 22% yield) of PTzPy as an orange powder: S.p.: 250 ºC. H NMR (in CDCl 3): δ = (2H, m, pyridyl), 7.65 (H, d, J = 4.0 Hz, thiophene), (2H, m, pyridyl), 8.7 (H, s, PTz), 8.7 (H, d, J = 4.0 Hz, thiophene). C NMR spectrum was not obtained because of low solubility of the product. HR-MS (APCI) Calcd for C 4H 7BrN 4S 2: [M+H] + : , Found: Synthesis of Ethyl 5-(trimethylstannyl)thiophene-2-carboxylate (a-2) Compound a-2 was obtained from ethyl thiopehen-2-carboxylate in a fashion similar to that of a- as a brown liquid in 92% yield. The H and C NMR spectra of the crude product showed its purity higher than 95% and the crude product was used for the following reaction without further purification: H NMR (in CDCl 3): δ = 0.40 (9H, s, Me 3Sn),.37 (3H, t, J = 6.8 Hz, CH 3), 4.34 (2H, q, J = 6.8 Hz, CH 2), 7.7 (H, d, J = 3.6 Hz, thiophene), 7.87 (H, d, J = 3.6 Hz, thiophene). C NMR (in CDCl 3): δ = -8.3, 4.4, 60.9, 3.9, 5.4, 9.2, 47.6, 62.. HR-MS (ESI) Calcd for C 0H 6O 2SSn: [M+Na] + : , Found: Synthesis of Ethyl 5-(7-bromo[,2,5]thiadiazolo[3,4-c]4-pyridyl)thiophene-2-carboxylate (PTzCO 2Et) A mixture of 362 mg (.23 mmol) of PTzBr2, 204 mg (.30 mmol) of a-2, 6.2 mg (5 mol%) of Pd 2(dba) 3, 74.6 mg (20 mol%) of P(o-tol) 3, and ml of toluene was heated at 60 ºC for 5 h with stirring. After usual workup using chloroform for extraction, the residue was purified by preparative GPC eluting with chloroform, followed by recrystallization from chloroform to give 29 mg (0.348 mmol, 27% yield) of PTzCO 2Et as a yellow powder: M.p.: ºC. H NMR (in CDCl 3): δ =.42 (3H, t, J = 6.8 Hz, CH 3), 4.4 (2H, q, J = 6.8 Hz, CH 2), 7.89 (H, d, J = 4.0 Hz, thiophene), 8.62 (H, d, J = 4.0 Hz, thiophene), 8.72 (H, s, PTz). C NMR (in CDCl 3): δ = 4.3, 6.6, 0.0, 2.0, 4.2, 7.7, 45.7, 46., 46.6, 47.9, 56.4, 62.. HR-MS (APCI) Calcd for C 2H 8BrN 3O 2S 2: 7

8 [M+H] + : , Found: Synthesis of 7-Bromo-4-[5-(4,4,5,5-tetramethyl-,3-dioxolan-2-yl)-2-thieyl]-[,2,5]thiadiazolo[3,4- c]pyridine (a-4) A mixture of 46 mg (0.496 mmol) of PTzBr2, 76 mg (0.59 mmol) of a-3, 30.9 mg (5 mol%) of Pd(PPh 3) 4,.0 ml of M Na 2CO 3 aq, and 0 ml of THF was heated at 70 ºC overnight with stirring. After usual workup using chloroform for extraction, the residue was subjected to silica gel chromatography eluting with hexane/ethyl acetate = 3/ to give 23 mg (0.288 mmol, 58% yield) of a-4 as a yellow powder: M.p.: 27-0 ºC. H NMR (in CDCl 3): δ =.33 (6H, s, CH 3),.36 (6H, s, CH 3), 6.22 (H, s, CH), 7.28 (H, d, J = 4.0 Hz, thiophene), 8.59 (H, d, J = 4.0 Hz, thiophene), 8.66 (H, s, PTz). C NMR (in CDCl 3): δ = 22., 24.2, 83.4, 96.6, 08.4, 27.6, 2.5, 4., 45.7, 47.5, 47.9, 49.8, HR-MS (APCI) Calcd for C 6H 6BrN 3O 2S 2: [M+H] + : , Found: Synthesis of 5-(7-Bromo-[,2,5]thiadiazolo[3,4-c]4-pyridyl)thiophene-2-carbaldehyde (PTzCHO) A powder of 23 mg (0.288 mmol) of a-4 was dissolved in 7 ml of 0% HCl aq and ml of THF and the mixture was heated to reflux overnight with stirring. After usual workup using chloroform for extraction, the residue was subjected to silica gel chromatography eluting with hexane/ethyl acetate = 5/ to give 83.5 mg (0.256 mmol, 89% yield) of PTzCHO as a yellow powder: M.p.: ºC. H NMR (in CDCl 3): δ = 7.88 (H, d, J = 4.0 Hz, thiophene), 8.73 (H, d, J = 4.0 Hz, thiophene), 8.76 (H, s, PTz), 0.02 (H, s, formyl). C NMR (in CDCl 3): δ = 0.8, 2.2, 6.6, 45.8, 46.2, 46.3, 47.9, 48.8, 56.4, HR-MS (APCI) Calcd for C 0H 4BrN 3OS 2: [M+H] + : , Found:

9 Current /μa Absorbance DTGPTzPy DTGPTzPy with 0.5mM CDCA DTGPTzCA DTGPTzCA with.0mm CDCA DTGPTzCA2 DTGPTzCA2 with 2.0mM CDCA Wavelength /nm Figure S2 Absorption spectra of DTG-containing dyes on TiO 2 films DTGPTzPy DTGPTzPy +TFA DTGPTzCA DTGPTzCA2 DTGPTzCA2 +TFA Voltage /V (Fc/Fc + ) Figure S3 Cyclic voltammograms (first cycle) of the DTG-containing dyes. 9

10 -Z'' /ohm DTGPTzPy DTGPTzCA DTGPTzCA Z' /ohm Figure S4 EIS Nyquist plots of DSSCs based on DTG-containing dyes. Figure S5 H NMR spectrum of DTGPTzPy in CD 2Cl 2. 0

11 Figure S6 H NMR spectrum of DTGPTzCA in CD 2Cl 2. Figure S7 H NMR spectrum of DTGPTzCA2 in DMSO-d 6.

12 [S] J. Ohshita, M. Miyazaki, F.-B. Zhang, D. Tanaka and Y. Morihara, Polym. J., 20, 45, 979. [S2] C.-G. Wu, W.-T. Shieh, C.-S. Yang, C.-J. Tan, C.-H. Chang, S.-C. Chen, C.-Y. Wu and H.-H. G. Tsai, Dyes and Pigments, 20, 99, 09. [S3] Y. Sun, S.-C. Chien, H.-L. Yip, Y. Zhang, K.-S. Chen, D. F. Zeigler, F.-C. Chen, B. Lin and A. K.-Y. Jen, J. Mater. Chem., 20, 2, 247. [S4] Y. Ooyama, S. Inoue, T. Nagano, K. Kushimoto, J. Ohshita, I. Imae and K. Komaguchi, Y. Harima, Angew. Chem. Int. Ed., 20, 50, [S5] V. Leandri, R. Ruffo, V. Trifiletti and A. Abbotto, Eur. J. Org. Chem., 20,