PDF《Supporting Information》

S1 Supporting Information Furan Fused V-Shaped Organic Semiconducting Materials with High Emission and High Mobility Katsumasa Nakahara,a Chikahiko Mitsui,b Toshihiro Okamoto,*,a,b,c Masakazu Yamagishi,b Takanari Ueno,d Yuji Tanaka,d Masafumi Yano,d Takeshi Matsushita,e Junshi Soeda,a,b Yuri Hirose,b Hiroyasu Sato,f Akihito Yamano,f Jun Takeya*,a,b a The Institute of Scientific and Industrial Research (ISIR), Osaka Univ.

, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan b Department of Advanced Materials Science, School of Frontier Sciences, The Univ. of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan. c JST, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan. d Faculty of Chemistry, Materials and Bioenginnering, Kansai Univ., 3-3-35 Yamate-cho, Suita, Osaka 564-8680, Japan e JNC Petrochemical Corp., 5-1 Goikaigan, Ichihara, Chiba 290-8551, Japan f Rigaku Corp., 3-9-12 Matsubara-cho, Akishima, Tokyo 196-8666, Japan Contents 1. Synthesis…S2 2. Ionization Potentials…S8 3. Absorption Spectra in Evaporated Thin Film and Solution…S9 4. Fluorescent Spectra…S11 5. Thermal Analyses…S13 6. Single-Crystal Analyses…S15 7. Theoretical Calculations…S16 8. Experimental Details for OFET Device Fabrication and Evaluation Procedure….S16 9. X-ray-diffraction Measurements for Solution-crystallized Thin Film……………S20 10. AFM Images of Solution-crystallized Thin Film…S21 11. References…S21 S2 1. Synthesis 1.1 Materials Reagents and Starting Materials 1.0 M Boron tribromide in dichloromethane,2-methoxy-6-bromonaphthalene and NiCl2(dppp) was purchased from TCI. All Grignard reagents, Fe(acac)3 and trimethoxy(2-phenylethyl)silane were purchased from SigmaCAldrich Inc. N-methylpyrrolidone, 1,2-dichlorobenzene were purchased from WAKO chemicals. 1.6 M n-BuLi in hexane and all anhydrous solvents were purchased from KANTO chemicals. Zeolite HSZ-360 was purchased from TOSOH Corp. 7-Methoxy-2-naphthyltrifluoromethanesulfonate1 and 6-decyl-2-methoxynaphthalene2 were prepared according to literature procedure. 1.2 Methods General for Synthesis and Characterization All the reactions were carried out under an atmosphere of nitrogen. Air- or moisture-sensitive liquids and solutions were transferred via a syringe or a Teflon cannula. Analytical thin-layer chromatography (TLC) was performed on glass plates with 0.25 mm 230C400 mesh silica gel containing a fluorescent indicator (Merck Silica gel

60 F254). TLC plates were visualized by exposure to ultraviolet lamp (254 nm and

365 nm) and by dipping with 10% phosphomolybdic acid in ethanol and heating on a hot plate. Flash column chromatography was performed on Kanto silica gel 60. Open column chromatography was performed on Wakogel C-200 (75C150 μm). All NMR spectra were recorded on a JEOL ECA600 and JEOL ECS400 spectrometers. Chemical shifts are reported in parts per million (ppm, δ scale) from residual protons in the deuterated solvent for

1 H NMR (δ?7.26 ppm for chloroform and δ?5.93 ppm for 1,1,2,2-tetrachloroethane) and from the solvent carbon for

13 C NMR (δ?77.16 ppm for chloroform and δ?74.00 ppm for 1,1,2,2-tetrachloroethane). The data were presented in the following format: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet), coupling constant in Hertz (Hz), signal area integration in natural numbers, assignment (italic). Mass spectra were measured on a JEOL JMS-T100LC APCI/ESI mass spectrometer. Melting points and elemental analyses were collected on a Mettler S3 Toledo MP70 Melting Point System and J-Science Lab JM10 MICRO CORDER, respectively. 1.3 Experimental Section 7-Decyl-2-methoxynaphthalene (Iron-catalyzed alkylation reaction3 ) To a solution of 7-methoxy-2-naphthyltrifluoromethanesulfonate (22.8 g, 74.4 mmol) and Fe(acac)3 (525 mg, 1.49 mmol,