Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2014. Supporting Information for Advanced Optical Materials, DOI: 10.1002/adom.201400078 Staggered Face-to-Face Molecular Stacking as a Strategy for Designing Deep-Blue Electroluminescent Materials with High Carrier Mobility Wen-Cheng Chen, Yi Yuan, Guang-Fu Wu, Huai-Xin Wei, Li Tang, Qing-Xiao Tong,* Fu-Lung Wong, and Chun-Sing Lee*
Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2013. Supporting Information Staggered Face-to-Face Molecular Stacking as A Strategy for Designing Deep-Blue Electroluminescent Materials with High Carrier Mobility Wen-Cheng Chen, Yi Yuan, Guang-Fu Wu, Huai-Xin Wei, Li Tang, Qing-Xiao Tong*, Fu- Lung Wong, and Chun-Sing Lee* General Information: 1 H NMR was recorded with a Varian Gemin-400 spectrometer. Mass spectra were recorded on a PE SCIEX API-MS spectrometer. Elemental analysis (C, H, N) was performed using a Vario EL III CHNS elemental analyzer. UV-vis absorption and PL spectra were measured on a Perkin-Elmer Lambda 950 UV/vis Spectrometer and a Perkin- Elmer LS50 fluorescence spectrometer, respectively. Ionization potentials (IP) of the materials were detected on ITO substrates in a thin-film state via ultraviolet photoelectron spectroscopy (UPS) in a VG ESCALAB 220i-XL surface analysis system, while electron affinitys (EA) were estimated by subtracting from IP with optical band gaps. Thermogravimetric analysis (TGA) and differential scanning calorimetric (DSC) were respectively performed on a TA Instrument TGAQ50 and a TA Instrument DSC2910. Crystallographic data collections of BBTPI and XBTPI were performed on an Oxford Diffraction Gemini E (Cu X-ray source, Kα, λ = 1.54178 Å for BBTPI and Mo X-ray source, Kα, λ = 0.71073 Å for XBTPI) equipped with a graphite monochromator and ATLAS CCD detector (CrysAlis CCD, Oxford Diffraction Ltd) at room temperature. The structures were solved by direct methods (SHELXTL-97), all non-hydrogen atoms were refined with anisotropic thermal parameters. BBTPI: 9,10-phenanthrenequinone (2.50 g, 12 mmol), [1,1':4',1''-terphenyl]-4,4''- dicarbaldehyde (BBCHO) (1.43 g, 5 mmol), 4-tert-butylbenzenamine (1.92 ml, 12 mmol), and ammonium acetate (7.71 g, 100 mmol) were added into glacial acetic acid (80 ml) and 1
the mixture refluxed for 24 h under an argon atmosphere. After cooling to room temperature, an orange-yellow mixture was obtained and poured into methanol under stirring. The crude product was separated by filtration, washed with methanol, and dried under vacuum. The product was purified by column chromatography (silica gel) using CH 2 Cl 2 as eluent to give a pale yellow solid, with an 81.8 % yield (3.79 g). 1 H NMR (400 MHz, CD 2 Cl 2, δ): 8.85 (s, 1H), 8.82 (d, J = 4.3 Hz, 2H), 8.80 (s, 1H), 8.76 (d, J = 8.2 Hz, 2H), 7.80-7.75 (m, 3H), 7.73 (t, J = 4.1 Hz, 8H), 7.70 (d, J = 8.5 Hz, 5H), 7.63 (d, J = 8.5 Hz, 4H), 7.54 (dd, J = 12.8, 7.7 Hz, 6H), 7.31 (t, J = 7.6 Hz, 2H), 7.25 (d, J = 7.3 Hz, 2H), 1.49 (s, 18H); MS (ESI) m/z: [M + H] + calcd for C 68 H 55 N 4, 927.4; found, 927.6. Anal. calcd for C 68 H 54 N 4 : C, 88.09; H, 5.87; N, 6.04; found: C, 88.02; H, 5.91; N, 6.04. XBTPI: The synthetic procedures were similar with BBTPI. Yield: 91.4 %. 1 H NMR (400 MHz, CD 2 Cl 2, δ): 8.87 (s, 2H), 8.81 (d, J = 8.4 Hz, 2H), 8.76 (d, J = 8.3 Hz, 2H), 7.78 (t, J = 7.4 Hz, 2H), 7.69 (d, J = 8.4 Hz, 10H), 7.59-7.48 (m, 6H), 7.37-7.23 (m, 8H), 7.16 (d, J = 2.5 Hz, 2H), 2.27 (d, J = 2.6 Hz, 6H), 1.47 (d, J = 2.8 Hz, 18H). MS (ESI) m/z: [M + H] + calcd for C 70 H 59 N 4, 955.5; found, 955.8. Anal. calcd for C 70 H 58 N 4 : C, 88.01; H, 6.12; N, 5.87; found: C, 88.09; H, 6.08; N, 5.81. Scheme S1. Synthetic procedures for BBTPI and XBTPI (a: Pd(PPh 3 ) 4, 4- formylphenylboronic acid, 2 M Na 2 CO 3, toluene, reflux; b: 9,10-Phenanthrenedione, 4-(tertbutyl)aniline, ammonium acetate, acetic acid, reflux) 2
Figure S1. The twisting molecular structures of a) BBTPI and b) XBTPI. Figure S2. The overlapped sections in the crystal of a) BBTPI and b) XBTPI. 3
Figure S3. Photoluminescent photos of BBTPI and XBTPI in a) dilute dichloromethane solution (10-6 mol L -1 ) and b) in solid state. Figure S4. Electric field dependent hole and electron mobility of the new compounds estimated by SCLC method. 4
Table S1. Crystallographic data and structure refinement for BBTPI and XBTPI. BBTPI XBTPI Empirical formula C 68 H 54 N 4 C 70 H 58 N 4 Formula weight 927.16 955.20 Temperature 293(2) K 293(2) K Wavelength 1.54178 0.71073 Crystal system, space group triclinic, P-1 triclinic, P-1 a = 7.2070(3) Å α= 116.304(3) a = 7.8514(7) Å α= 96.883(7) Unit cell dimensions b = 14.2438(6) Å b = 12.5846(11) Å β= 101.332(4) β= 100.702.(7) c = 15.2244(8) Å γ = 92.823(3) c = 14.8971(13) Å γ = 92.210(7) Volume 1357.10(11) Å 3 1433.1(2) Å 3 Z, Calculated density 1, 1.134 Mg/m 3 1, 1107 Mg/m 3 Absorption coefficient 0.504 mm -1 0.064 mm -1 F(000) 490 506 Crystal size 0.24 0.20 0.18 mm 0.28 0.24 0.16 mm Theta range for data collection 3.34 to 73.84 2.81 to 25.00 Reflections collected / unique 9708 / 5334 [R(int) = 0.0186] 12528 / 5038 [R(int) = 0.0763] Completeness to theta = 73.84 97.2 % 99.9 % Max. and min. transmission 0.9147 and 0.8886 0.9898 and 0.9823 Data / restraints / parameters 5334 / 37 / 325 5038 / 0 / 334 Goodness-of-fit on F 2 1.314 1.068 Final R indices [I > 2sigma(I)] R1 = 0.0961, wr2 = 0.2977 R1 = 0.1055, wr2 = 0.3062 R indices (all data) R1 = 0.1064, wr2 = 0.3301 R1 = 0.1898, wr2 = 0.3756 Largest diff. peak and hole 0.840 and -0.471 e. Å -3 1.017 and -0.312 e. Å -3 Table S2. Fitting parameters in SCLC measurements for BBTPI and XBTPI. Emitter Hole Electron µ 0 [10-4 cm 2 V -1 s -1 ] β [10-3 (V cm -1 ) -1/2 ] µ 0 [10-7 cm 2 V -1 s -1 ] β [10-3 (V cm -1 ) -1/2 ] BBTPI 25.6 ± 7.6 2.10 ± 0.77 6.1 ± 0.59 4.51 ± 0.92 XBTPI 4.2 ± 3.9 1.81 ± 0.59 4.49 ± 0.72 3.94 ± 0.74 Table S3. Key performance data for XBTPI- and BBTPI-based devices and other high efficiency nondoped blue light-emitting devices. Emitter V on [V] λ EL [nm] CE a) [cd A -1 ] PE b) [lm W -1 ] EQE c) [%] XBTPI 3.1 428 2.06, 2.01, 1.68 1.60, 1.32, 0.67 4.93, 4.80, 4.05 0.16, 0.05 This work TTP-TPI 3.1 424 2.10, -, 1.47 1.88, -, 0.81 5.02, -, 3.98 0.16, 0.05 22a TCPC-6-425 1.35, -, - -, -, - 3.72, -, - 0.16, 0.05 22b CzS1 3.5 426 1.89, 1.88, 1.45 1.58, 1.10, 0.57 4.21, 4.20, 3.19 0.157, 0.055 11 CzS2 2.8 417 0.82, 0.82, 0.73 0.84, 0.59, 0.33 2.70, 2.69, 2.20 0.157, 0.044 11 M1-420 0.65, -, - 0.48, -, - 1.94, -, - 0.165, 0.050 2b M2-428 1.53, -, - 0.86, -, - 3.02, -, - 0.166, 0.056 2b POAn 3.0 445 3.2, 3.0, - 3.3, 2.3, - 4.7, 4.5, - 0.15, 0.07 3b DPT-TPI 2.9 432 3.13, -, 2.78 3.22, -, 1.92 5.25, -, 4.62 0.16, 0.07 22a Be(PPI) 2 3.2-2.41, 2.18, 2.04 2.52, 1.60, 0.95 2.82, 2.55, 2.40 0.15, 0.09 10d Zn(PPI) 2 3.2-2.06, 1.31, 0.74 2.02, 0.75, 0.26 2.08, 1.32, 0.75 0.15, 0.09 10d CzPhB 6.5 449 3.3, -, - 1.3, -, - 4.3, -, - 0.15, 0.09 22c TPA-BPI 2.8 448 2.63, -, 2.42 2.53, -, 0.97 3.08, -, 2.88 0.15, 0.09 14a BBTPI 2.7 448 5.48, 5.35, 5.10 4.77, 4.41, 2.90 5.77, 5.60, 5.41 0.15, 0.10 This work DMPPP 4.5 446 5.2, -, - 1.9, -, - 5.2, -, - 0.15, 0.11 7b TPA-PPI - 434 5.66, 4.25, - 6.13, 2.7, - 5.02, 3.76, - 0.15, 0.11 14c TPVAn 4.9 456 5.3, 4.2, - 2.8, -, - 5.3, 4.2, - 0.14, 0.12 2a BD1 3.9 432 6.7, 6.1, 4.7 6.2, 4.9, 2.9 5.6, 5.0, 4.5 0.17, 0.13 22d B2PPQ 3.0 459 7.12, -, - 6.56, -, - 4.30, -, - 0.15, 0.16 3c BPPI 2.8 468 6.87, -, 6.74 6.2, -, 4.4 4.0, -, 3.9 0.16, 0.21 18 a) Current efficiency, b) power efficiency, c) external quantum efficiency corresponding to the value at the maximum, 100 cd m -2 and 1000 cd m -2, respectively. d) Parallel to main text. CIE [x, y] Ref. d) 5