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1 Ortho-substituent Effect on Fluorescence and Electroluminescence of Arylamino-substituted Coumarin and Stilbene Chao-Tsen Chen, *, Chih-Long Chiang, Yu-Chung Lin, Li-Hsin Chan, Chien-Huang Huang, Zong-Wei Tsai, Chin-Ti Chen *, Department of Chemistry, National Taiwan University, Taipei, Taiwan 6, R. O. C. Institute of Chemistry, Academia Sinica, Taipei, Taiwan 529, R. O. C. and Supporting Information Structural characterization of new coumarin and stilbene compounds. Electroluminescence characterizations of MeC and XTPS-based OLEDs. This material is available free of charge via the Internet at

2 General experimental informations. Merck silica gel 60F sheets were used for analytical thin-layer chromatography and column chromatography was performed on Kieselgel 60 ( mesh). Melting points were uncorrected. The Hand 3 CNMR spectra were obtained on Bruker spectrometers operating at frequencies as indicated for each compound. Chemical shifts are reported relative to CDCl 3 ( H 7.24) and at 77.0 ppm in CDCl 3 [ C (central line of t)]. Photospectroscopy. Absorption spectra were recorded on a Hewlett-Packard 8453A diode array spectrometer under the control of a Pentium PC running the manufacturer-supplied software package. Fluorescence spectra were obtained on a Hitachi F-4500 spectrometer. All solutions were prepared in spectroscopic grade of ethyl acetate without special efforts to exclude water or air. Electrochemistry. Oxidation potential of the compounds were determined by cyclic voltammetry (CV) using Electochemical Analyzer BAS B with a scanning rate either at mv/s. The compounds of interests were dissolved in deoxygenated dichloromethane containing tetrabutylammonium hexfluorophosphate (PhC, MeC, and ClC) orperchlorate(nsd, ATPS, TTPS, andxtps) as the electrolyte. A platinum working electrode and a saturated nonaqueous Ag/AgNO 3 reference electrode were used. Ferrocene was used for potential calibration (all reported potentials are referenced against ferrocene/ferrocenium, FOC) and for reversibility criteria. Structural characterization data of PhC: C 22 H 8 NO 2 ;mp=75 o C;R f =0.25(CH 2 Cl 2 /hexane, 70:30); H NMR (300 MHz, CDCl 3 ) δ (m, 5H), (m, 6H), 6.87 (dd, J=8.7, 2.2 Hz, H), 6.82 (d, J=2.2 Hz, H), 6.05 (s, H), 2.34 (s, 3H); 3 C{ H} NMR (75 MHz, CDCl 3 ) δ6.3, 54.89, 52.25, 5.24, 46., 29.64, 25.97, 24.93, 24.87, 6.47, 3.37, 7.6, 8.48; IR (KBr) 726.9, 67., 593.4, 494.2, 39.9, cm - ; FAB-MS: m/z 328. (M+H + ), FAB-HRMS for C 22 H 8 NO 2 Calcd ; Found ; Anal. Calcd for C 22 H 8 NO 2 : C, 80.7; H, 5.23; N, Found: C, 80.54; H, 5.04; N, 4.5. Anal. Found (Calcd) for C 22 H 8 NO 2 : C (80.7), H 5.04 (5.23), N 4.5 (4.28). 2

3 Structural characterization data of MeC: C 24 H 2 NO 2 : mp = o C;R f = 0.24 (EtOAc / hexane, :5); HNMR(400MHz, CDCl 3 ) δ7.3 (d, J = 8.4 Hz, H), (m, 2H), (m, 4H), 7.02 (d, J = 8.8 Hz, 2H), 6.50 (dd, J = 8.4,2.4 Hz, H), 6.42 (d, J = 2.4 Hz, H), 6.0 (s, H), 2.32 (s, 3H), 2.09 (s, 6H); 3 C{ H} NMR ( MHz, CDCl 3 ) δ6.35, 55.53, 52.24, 5.78, 44.26, 35.06, 3.99, 28.04, 27.40, 26.28, 25.06, 4.49, 2.53,.07, 4.73, 8.76, 8.35; IR (neat) , 302., , , 740., 65.3, 602., 549.6, 490.5, 39.9, 326.2, 273.7, 240.8, 48.9, 70.0 cm - ; FAB-MS: m/z (M + ), FAB-HRMS for C 24 H 2 NO 2 Calcd , Found ; Anal. Found (Calcd) for C 24 H 2 NO 2 : C (8.), H 5.96 (5.96), N 3.65 (3.94). Structural characterization data of ClC: C 22 H 5 Cl 2 NO 2 : mp = o C;R f = 0.3 (EtOAc / hexane, :5); HNMR(400MHz, CDCl 3 ) δ7.47 (dd, J = 7.4,.8 Hz, 2H), 7.36 (d, J = 8.7 Hz, H), (m, 6H), 6.49 (dd, J = 8.7,2.4 Hz, H), 6.4 (d, J = 2.4 Hz, H), 2.33 (s, 3H); 3 C{ H} NMR ( MHz, CDCl 3 ) δ6.42, 55.2, 52.49, 50.2, 4.86, 32.4, 3.36, 30.05, 28.36, 27.97, 25., 3.77, 3.3,.45, 4.4, 8.55; IR (neat) , 296.0, 733.5, 628.4, 589.0, 490.5, 39.9, 326.2, 293.4, 234.3, 55.4, 63.5, 30.6 cm - ; FAB-MS: m/z (M + ), FAB-HRMS for C 22 H 5 Cl 2 NO 2 Calcd , Found ; Anal. Found (Calcd) for C 22 H 5 Cl 2 NO 2 : C (66.68), H 3.85 (3.82), N 3.43 (3.53). Structural characterization data of ATPS: HNMR(400MHz,CDCl 3 ) 7.86 (s, H), (m, 7H), (m, 2H), (m, 5H); 3 C{ H} NMR ( 3

4 MHz, CDCl 3 ) 55.9,48.5, 42.0 ( 2), 4.7, 40.9, 40.7, 40.3, 40.0, 39.6, 39.60, 38.9, 35.7, 3.5, 3.3, 3., 29.9, 29.8, 29., 27.6, 27.3, 27.2, 26.8, 26.60, 26.57, 26.2, 25.8, 25.5, 25.3, 24.9, 20.3, 4.7, 55.5; FAB-MS: Calcd MW, 7.3, m/z = 7.5 (M + ). Anal. Found (Calcd) for C 52 H 4 NO 2 :C88.09 (87.73), H 5.78 (5.8), N 2.05 (.97). Structural characterization data of TTPS: HNMR(400MHz,CDCl 3 ) 7.84 (s, H), (m, 4H), (m, 5H), (m, 7H), 2.28 (s, 6H); 3 C{ H} NMR ( MHz, CDCl 3 ) 47.7, 45.0 ( 2), 42.0, 4.7, 40.9, 40.2, 40.0, 39.7, 39.6, 39.0, 35.7, 32.7, 3.5, 3.3, 3., 30.8, 29.90, 29.86, 29., 27.6, 27.30, 27.25, 26.8, 26.6, 26.2, 25.9, 25.5, 25.4, 25.3, 24.8, 22.2, 20.8; FAB-MS: Calcd MW, , m/z = (M + ). Anal. Found (Calcd) for C 52 H 4 N: C, 9.6 (9.86), H, 5.9 (6.08), N,.88 (2.06). Structural characterization data of XTPS: H NMR (400 MHz, CDCl 3 ): 7.82 (s, H), (m, 3H), (m, 3H), (m, 5H), (m, 7H), (m, 2H), 6.70 (d, 2H, 6. Hz), 6.48 (d, 8.7 Hz), 2.27 (s, 6H),.97 (s, 6H); 3 C{ H} NMR ( MHz, CDCl 3 ) 48.8, 43.0(X2), 42., 4.6, 40.9, 40.3, 40.0, 39.64, 39.60, 38.8, 35.8, 34.5,34.48, 32.2, 3.5, 3.3, 3., 29.9, 29.2, 28.9, 27.6, 27.58, 27.4, 27.27, 27.25, 26.8, 26.6, 26.2, 25.8, 25.5, 25.3, 24.4, 8.8, 20.9, 8.8; FAB-MS: Calcd MW, , m/e = (M + ). Anal. Found (Calcd) for C 54 H 44 N: C 9.62 (9.6), H 6.45 (6.4), N 2.00 (.98). 4

5 ITO/NPB (40 nm)/mec (30 nm)/tpbi (40 nm)/mg 0.9 :Ag nm Intensity (a.u.) fwhm = 72 nm Wavelength (nm) Current density (ma/cm 2 ) E Luminescence (cd/m 2 )

6 ITO/XTPS (60 nm)/tpbi (40 nm)/mg 0.9 :Ag nm Intensity (a.u.) fwhm = 72 nm Wavelength (nm) Current density (ma/cm 2 ) E Luminescence (cd/m 2 )