Synlett 2013; 24(15): 1988-1992
DOI: 10.1055/s-0033-1339481
letter
© Georg Thieme Verlag Stuttgart · New York

Facile Synthesis of [6,6]-Phenyl-C61/71-Butyric Acid Methyl Esters via Sulfur Ylides for Bulk-Heterojunction Solar Cell

Takatoshi Ito*
Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan   Fax: +81(6)69638049   Email: [email protected]   Email: [email protected]
,
Toshiyuki Iwai
Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan   Fax: +81(6)69638049   Email: [email protected]   Email: [email protected]
,
Fukashi Matsumoto
Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan   Fax: +81(6)69638049   Email: [email protected]   Email: [email protected]
,
Koichi Hida
Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan   Fax: +81(6)69638049   Email: [email protected]   Email: [email protected]
,
Kazuyuki Moriwaki
Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan   Fax: +81(6)69638049   Email: [email protected]   Email: [email protected]
,
Yuko Takao
Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan   Fax: +81(6)69638049   Email: [email protected]   Email: [email protected]
,
Takumi Mizuno
Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan   Fax: +81(6)69638049   Email: [email protected]   Email: [email protected]
,
Toshinobu Ohno*
Osaka Municipal Technical Research Institute, 1-6-50, Morinomiya, Joto-ku, Osaka 536-8553, Japan   Fax: +81(6)69638049   Email: [email protected]   Email: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 10 May 2013

Accepted after revision: 02 July 2013

Publication Date:
14 August 2013 (online)


Abstract

A one-step, mild synthesis of methanofullerenes as electron acceptors for solution-processed bulk-heterojunction solar cells was developed. [6,6]-Phenyl-C61-butyric acid methyl ester {[60]PCBM} was directly synthesized in good yields, by the reaction of fullerene with sulfur ylide derivatives in the presence of 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) at room temperature. This method was also successfully applied to the preparation of [6,6]-phenyl-C71-butyric acid methyl ester {[70]PCBM}.

 
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  • 18 Preparation of [6,6]-Phenyl-C61-butyric Acid Methyl Ester {[60]PCBM}7b To a stirred mixture of sulfonium salt 2b (85 mg, 0.25 mmol) and fullerene C60 (100 mg, 0.14 mmol) in ODCB (7 mL) was added DBU (46 mg, 0.30 mmol) in one portion at r.t. After stirring for 6 h, AcOH (ca. 3 equiv) was added. The reaction mixture was concentrated to ca. 3 mL under reduced pressure. The residue was purified by silica gel column chromatography {eluent, stepwise gradient of CH2Cl2 (0–80%) in toluene}. The obtained product was dissolved in a small amount of toluene and poured into MeOH. The resulting suspension was centrifuged, and the supernatant was decanted. The product was dried in vacuo at 60 °C. [60]PCBM was obtained in 45% isolated yield (57 mg). Unreacted C60 (22 mg, 22%) and bisadducts (8 mg, 5%) were isolated in the same manner. 1H NMR (300 MHz, CDCl3): δ = 7.92 (d, J = 8.7 Hz, 2 H), 7.60–7.44 (m, 3 H), 3.68 (s, 3 H), 2.94–2.88 (m, 2 H), 2.52 (t, J = 7.5 Hz, 2 H), 2.23–2.13 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 173.40, 148.79–136.71, 132.06, 128.43, 128.24, 79.87, 51.85, 51.64, 33.87, 33.67, 22.37. IR (KBr): 2921, 2849, 1735, 699, 573, 550, 526, 482, 453 cm–1. MS (MALDI): m/z calcd for C72H14O2: 910.1; found: 910.1 [M]+.
  • 19 Troshin PA, Hoppe H, Peregudov A, Egginger SM, Shokhovets S, Gobsch G, Sariciftci NS, Razumov VF. ChemSusChem 2011; 1194
  • 20 [6,6]-Phenyl-C71-butyric Acid Methyl Ester {[70]PCBM}7b 1H NMR (300 MHz, CDCl3): δ = 7.92–7.40 (m, 5 H), 3.74 (minor isomer, s, 0.26 H), 3.67 (major isomer, s, 2.55 H), 3.51 (minor isomer, s, 0.19 H), 2.53–2.42 (m, 4 H), 2.25–1.99 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 173.38, 149.43–128.20, 69.82, 51.68, 33.80, 21.70. IR (KBr): 2941, 2923, 1737, 1429, 795, 726, 699, 674, 643, 579, 534, 459 cm–1. MS (MALDI): m/z calcd for C72H14O2: 1030.1; 1030.2 [M]+.
  • 21 Bis[70]PCBM To a stirred mixture of sulfonium salt 2b (51 mg, 0.15 mmol) and fullerene C70 (25 mg, 0.030 mmol) in ODCB (12 mL) was added DBU (23 mg, 0.15 mmol) in one portion at r.t. After stirring for 7 h, AcOH (ca. 3 equiv) was added and treatments in the same manner of ref. 18, bis[70]PCBM was obtained in 64% isolated yield (23 mg). Unreacted C70 (0.6 mg, 2%) and monoadducts (7.5 mg, 24%) were isolated.1H NMR (300 MHz, CDCl3): δ = 7.93–7.37 (m, 5 H), 3.67–3.65 (m, 3 H), 2.50–2.10 (m, 6 H). MS (MALDI): m/z calcd for C72H14O2: 1220.2; found: 1220.2 [M]+. Spectroscopic data were in good agreement with the literature: Lenes M, Shelton SW, Sieval AB, Kronholm DF, Hummelen JC, Blom PW. M. Adv. Funct. Mater. 2009; 19: 3002