Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2018 Electronic Supporting Information (ESI) for Effect of Conjugation and Aromaticity of 3,6 Di-substituted Carbazole On Triplet Energy Kai Lin Woona* , Azhar Ariffinb**, Kar Wei Hob, Show-An Chenc a Low Dimensional Materials Research Center, Department of Physics, University of Malaya, Malaysia b Department of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia c Department of Chemical Engineering and Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing-Hua University, 101, Section 2, Kuang-Fu Road, 30041 Hsinchu, Taiwan, ROC Contents I General methods………………………………………………………………………… 1 II Synthesis procedures …………………………………………………………………… 2 III Copies of 1H, 13C NMR and mass spectrum for synthesized compounds ………… 13 IV Torsional Angle ……………………………………………………………………….. 32 V Coordinates of Stationary Points in xyz format ……………………………………… 33 I. General methods Proton and carbon nuclear magnetic resonance spectroscopy (1H NMR and 13C NMR spectra) were obtained on a Bruker AVANCE III 400 MHz FT-NMR spectrometer using deuterated chloroformas the solvent with tetramethylsilane (TMS) as internal standard. Matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) measurements were carried out with a Bruker Microflex series spectrometer in order to measure the molecular masses. 2,5-dihydroxybenzoic acid (DHB) was used as matrix. 2 II. Synthesis procedures Bis(4-bromophenyl)diphenylsilane, (1), Known compound. Br Si Br Compound 1 was prepared according to modified procedure from the literature.20 1,4- Dibromobenzene (4.20 g, 17.8 mmol) was dissolved in 15mL dry THF under nitrogen atmosphere. The solution was cooled to -78 °C. 9.6 mL of n-BuLi (2.0 M in cyclohexane) was added dropwise and stir for 1 h. Dichlorodiphenylsilane (1.68 mL, 8 mmol) was added slowly at -78 °C. The mixture was stirred overnight while allowing the temperature to rise to room temperature. The reaction was then quenched with water and extracted with chloroform. The organic layer was dried over anhydrous sodium sulfate. After the solvent was evaporated, the crude product was purified by recrystallization from ethanol to afford white solid (2.54 g, 64.3 %). Melting point = 160-162 C. 1HNMR (CDCl , 400 MHz): δ (ppm) 3 = 7.57-7.52 (m, 8H), 7.48-7.38 (m, 10H). 13C NMR (CDCl , 100 MHz): δ (ppm) = 137.93, 136.32, 3 134.98, 133.36, 131.14, 129.88, 128.02, 124.82. 3,6-Diiodocarbazole, (2), Known compound. I I N H Carbazole (8.36 g, 50 mmol) was dissolved in boiling acetic acid (200 mL). To the solution, potassium iodide (10.8 g, 50 mmol) was added. The solution was cooled and potassium iodate (21.5 g, 50 mmol) was added. Solution was refluxed at 80 ºC for 1 h. The solution was decanted from undissolved potassium iodate and it was allowed to cool to room temperature. The crude product obtained was filtered and recrystallized from dichloromethane to give brown solid (13.97 g, 66.7%). Melting point = 208 - 210 C. 1H NMR (CDCl , 400 MHz): δ (ppm) = 8.36 (s, 2H), 8.14 (br, s, 1H), 7.71 (dd, 2H, J=8.50, 3 1.65 Hz), 7.24 (d, 2H, J=8.56 Hz). 13C NMR (CDCl , 100 MHz): δ (ppm) = 138.53, 134.83, 129.40, 3 124.58, 112.70, 82.44. 3 3,6-bis(4-(tert-butyl)phenyl)-9H-carbazole, (3), Known compound. N H Compound 3 was prepared using Suzuki coupling reaction. 4-Tert-butylphenylboronic acid (1.1 g, 6.2 mmol) and compound 4 (1.25 g, 3 mmol) were dissolved in 25 ml toluene in a round bottom flask under nitrogen. A solution of potassium carbonate (2M, 1.7 ml) was added to the solution. tetrakis(triphenyl- phosphine)palladium(0) (0.14 g, 0.12 mmol) was added. The reaction mixture was reflux for 24 h under nitrogen. After cooling to room temperature, the reaction mixture was evaporated to remove solvent and extracted with chloroform and water. The organic layer was removed under reduced pressure, and the residue was subjected to a column chromatography using hexane/ethyl acetate as the eluent to obtain white solid (yield 85.6%, 1.11 g). Melting point , decompose > 200 C 1H NMR (400 MHz, CDCl ) δ 3 [ppm]: 8.34 (d, J=1.71 Hz, 2H), 8.13 (s, 1H), 7.66 – 7.73 (m, 6H), 7.49 – 7.56 (m, 6H), 1.42 (s, 18H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 149.46, 139.30, 139.16, 132.99, 126.92, 125.72, 125.52, 124.04, 3 118.71, 110.85, 34.51, 31.44. HRMS (MALDI-TOF) m/z: [M]+ Calcd for C H N 431.2613; Found 32 33 431.165. 3,6-bis(3-methoxyphenyl)-9H-carbazole (4), known compound. O O N H Compound 4 was prepared using Suzuki coupling reaction. 3-Methoxyphenylboronic acid (3.17 g, 20.9 mmol) and compound 2 (3.98 g, 9.49 mmol) were dissolved in 40 ml toluene in a round bottom flask under nitrogen. A solution of potassium carbonate (2M, 10 ml) was added to the solution. tetrakis(triphenyl-phosphine)palladium(0) (0.47 g, 0.41 mmol) was added. The reaction mixture was reflux for 24 h under nitrogen. After cooling to room temperature, the reaction mixture was evaporated to remove solvent and extracted with chloroform and water. The organic layer was removed under 4 reduced pressure, and the residue was subjected to a column chromatography using hexane/ethyl acetate as the eluent to obtain white solid 6 (yield 17.4%, 0.63 g). Melting point , decompose > 200 C. 1H NMR (400 MHz, CDCl ) δ [ppm]: 8.36 (d, J=1.83 Hz, 2H), 8.17 (s, 1H), 7.72 (dd, J=8.24, 1.83 Hz, 2H), 3 7.53, (d, J=8.24 Hz, 2H), 7.38 – 7.48 (m, 2H), 7.31 – 7.37 (m, 2H), 7.24 – 7.31 (m, 2H), 6.87 – 7.00 (m, 2H), 3.94 (s, 6H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 160.07, 143.63, 139.58, 133.12, 129.83, 125.75, 3 124.05, 119.93, 119.04, 113.06, 112.09, 110.99, 55.44. HRMS (MALDI-TOF) m/z: [M]+ Calcd for C H NO 379.1572; Found 378.868. 26 21 2 3,6-bis(4-fluorophenyl)-9H-carbazole, (5), known compound. F F N H Compound 5 was prepared using Suzuki coupling reaction. 4-fluorophenylboronic acid (0.93 g, 6.7 mmol) and compound 2 (1.27 g, 3.03 mmol) were dissolved in 24 ml toluene in a round bottom flask under nitrogen. A solution of potassium carbonate (2M, 6 ml) was added to the solution. tetrakis(triphenyl-phosphine)palladium(0) (0.13 g, 0.11 mmol) was added. The reaction mixture was reflux for 24 h under nitrogen. After cooling to room temperature, the reaction mixture was evaporated to remove solvent and extracted with chloroform and water. The organic layer was removed under reduced pressure, and the residue was subjected to a column chromatography using hexane/ethyl acetate as the eluent to obtain white solid 7 (yield 30.4%, 0.33 g). Melting point , decompose > 200 C. 1H NMR (400 MHz, CDCl ) δ [ppm]: 8.29 (s, 2H), 8.17 (br. s., 1H), 7.62 – 7.72 (m, 6H), 7.53 (d, J=8.44 3 Hz, 2H), 7.19 (t, J=8.68 Hz, 4H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 163.34, 160.90, 139.36, 138.15, 3 132.32, 128.80, 128.71, 125.58, 123.97, 118.79, 115.69, 115.48, 111.01. HRMS (MALDI-TOF) m/z: [M]+ Calcd for C H F N 355.1173; Found 355.779. 24 15 2 3,6-bis(4-methoxyphenyl)-9H-carbazole, (6), known compound. MeO OMe N H Compound 6 was prepared using Suzuki coupling reaction. 4-methoxyphenylboronic acid (1.31 g, 8.6 mmol) and compound 2 (1.51 g, 3.6 mmol) were dissolved in 30 ml toluene in a round bottom flask 5 under nitrogen. A solution of potassium carbonate (2M, 3.6 ml) was added to the solution. tetrakis(triphenyl-phosphine)palladium(0) (0.17 g, 0.14 mmol) was added. The reaction mixture was reflux for 24 h under nitrogen. After cooling to room temperature, the reaction mixture was evaporated to remove solvent and extracted with chloroform and water. The organic layer was removed under reduced pressure, and the residue was subjected to a column chromatography using hexane/ethyl acetate as the eluent to obtain white solid 8 (yield 43.5%, 1.13 g). Melting point = 198-200 C 1H NMR (600 MHz, CDCl ) δ [ppm]: 8.30 (s, 2H), 8.10 (br. s., 1H), 7.60 – 7.78 (m, 6H), 7.50 (d, J=8.25 Hz, 2H), 6.97 3 – 7.09 (m, 4H), 3.90 (s, 6H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 158.65, 139.10, 134.74, 132.82, 3 128.27, 125.32, 124.05, 118.43, 114.24, 110.85, 55.40. HRMS (MALDI-TOF) m/z: [M]+ Calcd for C H NO 379.1572; Found 379.511. 26 21 2 3,6-diiodo-9-tosyl-9H-carbazole, (8), known compound. O S O N I I Compound 8 was prepared according to procedure from the literature. 2 To a solution of compound 2 (2.01 g, 4.8 mmol) in N,N-dimethylformamide (20 ml) was added sodium hydride (0.84 g, 35 mmol) at 0 ºC, and stirred for 10 mins. Subsequently, p-toluenesulfonyl chloride (2.9 g, 15.8 mmol) was added to this mixture and stirred at 0ºC for 4 h. the mixture was diluted with water and the precipitates were filtered. The crude product was recrystallized from dichloromethane to afford compound 8 (3.0 g, 62.4 %) as white solid. Melting point , decompose > 250 C 1H NMR (400 MHz, CDCl ) δ [ppm]: 8.20 (d, 3 J=1.59 Hz, 2H), 8.10 (d, J=8.80 Hz, 2H), 7.80 (dd, J=8.74 Hz, 2H), 7.67 (d, J=8.44 Hz, 2H), 7.16 (d, J=8.07 Hz, 2H), 2.32 (s, 3H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 145.49, 137.82, 136.55, 134.43, 3 129.90, 129.17, 127.19, 126.46, 116.98, 87.96, 21.56. HRMS (MALDI-TOF) m/z: [M]+ Calcd for C H I NO S 572.8756; Found 572.885. 19 13 2 2 3,6-di-tert-butyl-9H-carbazole, (7), known compound. N H 6 In ice bath of 0 ºC, carbazole (20 mmol) was suspended in 100 ml chloroformunder nitrogen. AlCl (2.67 3 g, 20 mmol) was added in portions. Tert-butyl chloride (5.3 ml, 24 mmol) was then added drop wise. Then the mixture was stirred for 12 h. The reaction was quenched by ice water, and extracted by chloroform. The organic layer was dried with anhydrous Na SO and the solvent was removed under 2 4 reduced pressure to obtain white solid. Yield: 82.6%. Melting point = 230-233 C. 1H NMR (400 MHz, CDCl ) δ [ppm]: 8.10 (s, 2H), 7.88 (br. s., 1H), 7.49 (d, J=8.44 Hz, 2H), 7.36 (d, J=8.44 Hz, 2H), 1.48 3 (s, 18 H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 142.24, 138.02, 123.52, 123.33, 116.18, 109.98, 34.69, 3 32.04. HRMS (MALDI-TOF) m/z: [M]+ Calcd for C H N 279.1987; Found 279.235. 20 25 3,3'',6,6''-tetrakis(4-methoxyphenyl)-9'-tosyl-9'H-9,3':6',9''-tercarbazole (9), New compound. O S O N N N O O O O Compound 9 was prepared according to procedure from the literature. 1 A solution of compound 8 (1.16 g, 2.03 mmol) and compound 6 (1.68 g, 4.42 mmol) in N,N-dimethylacetamide (10 ml) was prepared. Copper oxide (0.59 g, 4.1 mmol) was added to the solution. The mixture was then refluxed for 48 h and cooled to room temperature. After cooling to room temperature, the reaction mixture was evaporated under reduced pressure to remove solvent and extracted with chloroform and water. The organic layer was evaporated under reduced pressure, and the residue was subjected to a column chromatography using hexane/ethyl acetate as the eluent to obtain white solid with (yield 49.1 %, 1.07 g). Melting point , decompose > 300 C. 1H NMR (400 MHz, CDCl ) δ [ppm]: 8.66 (d, J=8.80 Hz, 2H), 8.36 (d, J=1.35 3 Hz, 4H), 8.18 (d, J=1.83 Hz, 2H), 7.98 (d, J=8.44 Hz, 2H), 7.83 (dd, J=8.93, 2.08 Hz, 2H), 7.66 (d, J=8.80 Hz, 8H), 7.63 (dd, J=8.25, 1.83 Hz, 4H), 7.46 (d, J=8.56 Hz, 4H), 7.35 (d, J=8.07 Hz, 2H), 7.04 (d, J=8.80 Hz, 8H), 3.90 (s, 12H), 2.44 (s, 3H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 158.75, 140.74, 3 137.71, 135.05, 134.51, 134.08, 133.51, 130.17, 128.35, 128.29, 127.06, 126.82, 125.49, 125.46, 124.09, 118.88, 118.50, 116.47, 114.28, 109.87, 55.41, 21.73. HRMS (MALDI-TOF) m/z: [M]+ Calcd for 7 C H N O S 1075.3655; Found 1075.875. 71 53 3 6 3,3'',6,6''-tetra-tert-butyl-9'-tosyl-9'H-9,3':6',9''-tercarbazole (10), Known compound. O S O N N N Compound 10 was prepared according to procedure from the literature. 1 A solution of compound 8 (1.44 g, 2.51 mmol) and compound 7 (1.54 g, 5.5 mmol) in N,N-dimethylacetamide (10 ml) was prepared. Copper oxide (0.73 g, 5.1 mmol) was added to the solution. The mixture was then refluxed for 48 h and cooled to room temperature. After cooling to room temperature, the reaction mixture was evaporated under reduced pressure to remove solvent and extracted with chloroform and water. The organic layer was evaporated under reduced pressure, and the residue was subjected to a column chromatography using hexane/ethyl acetate as the eluent to obtain white solid with yield of 65.5% (1.44 g). Melting point = decompose > 300 C. 1H NMR (600M Hz, CDCl ) δ [ppm]: 8.59 (d, J=8.80 Hz, 2H), 8.16 (d, J=1.65 3 Hz, 4H), 8.07 (d, J=2.02 Hz, 2H), 7.94 (d, J=8.25 Hz, 2H), 7.75 (dd, J=8.80, 2.20 Hz, 2H), 7.47 (dd, J=8.62, 2.02 Hz, 4H), 7.35 (d, J=8.25 Hz, 4H), 7.32 (d, J=8.25 Hz, 2H), 2.42 (s, 3H), 1.48 (s, 36H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 145.49, 143.02, 139.51, 137.38, 135.02, 134.54, 130.07, 127.09, 3 126.77, 123.70, 123.38, 118.50, 116.32, 108.97, 34.74, 32.00, 21.69. HRMS (MALDI-TOF) m/z: [M]+ Calcd for C H N O S 875.4484; Found 875.756. 59 61 3 2 3,3'',6,6''-tetrakis(4-methoxyphenyl)-9'H-9,3':6',9''-tercarbazole (11), New compound. H N N N O O O O Compound 11 was prepared according to the procedure from the literature. 1 To a solution of compound 9 (1.04 g, 0.965 mmol) in 9 ml tetrahydrofuran were added dimethyl sulfoxide (2.45 ml) and water (1.0 8 ml), and the mixture was stirred for 10 mins. Subsequently, potassium hydroxide (1.36 g, 0.024 mol) was added to this mixture, and the reaction mixture was refluxed for 4 hours, cooled to room temperature and diluted with water. After neutralization with HCl solution, the crude product was filtered and recrystallized from dichloromethane-hexane (1:1) to give compound 11 as white solid (yield 99.4 %, 0.884 g). Melting point , decompose > 300 C, 1H NMR (600 MHz, CDCl ) δ [ppm]: 8.62 (br. s., 1H), 3 8.25 – 8.44 (m, 6H), 7.40 – 7.82 (m, 20H), 7.04 (d, J=8.80 Hz, 8H), 3.89 (s, 12H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 158.66, 146.60, 141.42, 139.33, 134.73, 130.06, 128.30, 126.11, 125.35, 123.82, 3 120.44, 119.70, 118.41, 114.25, 112.13, 110.03, 55.40. HRMS (MALDI-TOF) m/z: [M]+ Calcd for C H N O 921.3567; Found 921.795. 64 47 3 4 3,3'',6,6''-tetra-tert-butyl-9'H-9,3':6',9''-tercarbazole (12), Known compound. H N N N Compound 12 was prepared according to the procedure from the literature. 1 To a solution of compound 10 (1.39 g, 1.59 mmol) in 10 ml tetrahydrofuran were added dimethyl sulfoxide (4.8 ml) and water (1.6 ml), and the mixture was stirred for 10 mins. Subsequently, potassium hydroxide (1.59 g, 0.03 mol) was added to this mixture, and the reaction mixture was refluxed for 4 hours, cooled to room temperature and diluted with water. After neutralization with HCl solution, the crude product was filtered and recrystallized from dichloromethane-hexane (1:1) to give compound 12 as white solid (yield 99.5%, 1.14 g). Melting point , decompose > 300 C. 1H NMR (600 MHz, CDCl ) δ [ppm]: 8.52 (br. s., 1H), 8.18 3 (d, J=1.65 Hz, 6H), 7.70 (d, J=8.16 Hz, 2H), 7.63 (dd, J=8.48, 1.88 Hz, 2H), 7.47 (dd, J=8.57, 1.65 Hz, 4H), 7.33 (d, J=8.07 Hz, 4H), 1.48 (s, 36H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 142.50, 140.19, 3 139.07, 125.97, 124.11, 123.54, 123.07, 119.43, 116.18, 111.84, 109.11, 102.16, 34.73, 32.05 HRMS (MALDI-TOF) m/z: [M]+ Calcd for C H N 721.4396; Found 721.654. 52 55 3 Bis(4-(3,6-bis(4-(tert-butyl)phenyl)-9H-carbazol-9-yl)phenyl)diphenylsilane, P1, New compound. 9 N Si N Compound 1 (0.25 g, 0.51 mmol), carbazole 3 (0.48 g, 1.12 mmol), copper powder (0.13 g, 2.05 mmol), and 18-Crown-6 (0.013 g, 0.049 mmol) and K CO (0.55 g, 4.0 mmol) were dissolved in 4 ml 2 3 anhydrous o-dichlorobenzene under nitrogen atmosphere. The reaction mixture was refluxed for 72 h at 180 ºC. After cooling to room temperature, the mixture was diluted in dichloromethane and filtered through silica gel. The filtrate was evaporated under reduced pressure to give crude product, which purified through column chromatography to give white powdery product (yield 20.1 %, 0.123g). Melting point , decompose > 300 C. 1H NMR (400 MHz, CDCl ) δ [ppm]: 8.41 (d, J=1.47 Hz, 4H), 7.95 (d, 3 J=8.31 Hz, 4H), 7.46 – 7.80 (m, 38H), 1.42 (s, 36H). 13C NMR (100 MHz, CDCl ) δ [ppm]: 149.63, 3 140.32, 139.26, 138.98, 137.99, 136.48, 133.71, 133.55, 133.23, 130.09, 128.24, 126.95, 126.11, 125.77, 125.61, 124.25, 118.71, 110.25, 34.52, 31.43. HRMS (MALDI-TOF) m/z: [M]+ Calcd for C H N Si 88 82 2 1194.6247; Found 1195.097. Bis(4-(3,6-bis(3-methoxyphenyl)-9H-carbazol-9-yl)phenyl)diphenylsilane, P2. New compound. O O N Si N O O Compound 1 (0.20 g, 0.404 mmol), carbazole 4 (0.33 g, 0.86 mmol), copper powder (0.10 g, 1.57 mmol), and 18-Crown-6 (0.011 g, 0.042 mmol) and K CO (0.44 g, 3.2 mmol) were dissolved in 4 ml anhydrous 2 3 o-dichlorobenzene under nitrogen atmosphere. The reaction mixture was refluxed for 72 h at 180 ºC. After cooling to room temperature, the mixture was diluted in dichloromethane and filtered through silica gel. The filtrate was evaporated under reduced pressure to give crude product, which purified through column chromatography to give white powdery product (yield 27.7%, 0.122 g). Melting point , 10