A mesogenic triphenylene-perylene-tri phenylene triad

Transcription

1 Supporting information A mesogenic triphenylene-perylene-tri phenylene triad Xiangfei Kong a, Zhiqun He a, Yinning Zhang a, Linping Mu a, Chunjun Liang a, Xiping Jing b, Andrew Cammidge c * Experimental procedures for synthesis and MR spectra 2 Absorption and Fluorescence spectra for PBITP

2 Experimental Section 1. Instrumentation 1 H and 13 C MR spectra were measured at 200 MHz, 300 MHz and 400MHz MR (Varian). ptical absorption spectra were recorded using a UV-Vis spectrophotometer (PerkinElmer Lambda 35) or IR spectrometer (Vector 22). High resolution mass spectra (HRMS) were obtained via a Bruker Apex IV FTMS. A cross-polarized optical microscope (Leica DMRX) was used along with a hot stage (Linkam THMSE 600) to examine phase transitions. Thermal analysis of the materials was carried out using a differential scanning calorimeter (DSC) (Thermal Analysis Q100) at a scanning rate of 10 C/min under 2 atmosphere. 2. Chemicals and synthetic procedures 1 Monhydroxypentahexyloxytriphenylene was prepared as previously reported. Phthalimide (4) (analytical grade) was purchased from Beijing Reagent Plant. 3,4,9,10-perylenetetracarboxylic dianhydride (19) (99%) was purchased from Sigma Aldrich. Potassium phthalimide (5) Phthalimide (4) (20 g, mol) was added to 400ml absolute ethanol. The mixture was gently heated under reflux and then the hot solution was decanted into a solution of potassium hydroxide (7.6 g, mole) in water (7.5 ml) and ethanol (23 ml). The mixture was stirred and cooled quickly to room temperature, and the precipitate was filtered with suction. The crystals obtained were washed with 12ml of acetone twice to remove any unchanged phthalimide. The yield of air-dried potassium phthalimide is 18.6 g. (82%). -(2-Bromoethyl)phthalimide(6) The mixture of potassium phthalimide(5) (3g, 16.1mmol) and 1,2-dibromoethane (12.1g, 64.4mmol) was stirred and heated for 12 h in an oil bath maintained at The condenser was then set for distillation, and the excess 1,2-dibromoethane was distilled under reduced pressure. The crude product was purified by column chromatography (silica gel, dichloromethane/light petroleum 2:3) and afforded a colorless solid (2.87g, 70%). Mp C. 1 H MR (CDCl 3, 300MHz) ( 1 )Kong, X.; He, Z.; Gopee, H.; Jing, X.; Cammidge, A.. Tetrahedon Lett. 2011, 52, K Br 2

3 (m, 2H), (m, 2H), 4.09 (t, 2H, J = 6.9 Hz), 3.60 (t, 2H, J = 6.9 Hz). 13 C MR (CDCl 3, 50MHz) , , , , 39.20, MS: (EI) 160 (100%), 253 (M + )11%, 255 (M + )10%. Elemental analysis calcd for C 10 H 8 Br 2 (254):, 5.51; C, 47.27; H, 3.17; Found:, 5.49; C, 47.27; H, (4-Bromobutyl)phthalimide(7) A mixture of potassium phthalimide 5 (0.93 g, 5 mmol) and 1,4-dibromobutane (5.4 g, 25 mmol) was stirred in dry DMF (10ml) at 100 for 12 h. The condenser was then set for distillation, and the excess of 1,4-dibromobutane and DMF were distilled under reduced pressure. The crude product was purified by column chromatography (silica gel, ethyl acetate/light petroleum 1:50) and afforded a colorless solid (1.23g, 87%). Mp C. 1 H MR (CDCl 3, 300MHz) (m, 2H), (m, 2H), 3.73 (t, 2H, J = 6.9 Hz), 3.45 (t, 2H, J = 6.9 Hz), (m, 4H). 13 C MR (CDCl 3, 75MHz) , , , , 36.90, 32.82, 29.76, MS: (EI) 160 (100%), 202 (36%), 281 (M + ) 5%, 283 (M + ) 4%. Elemental analysis calcd for for C 12 H 12 Br 2 (282):, 4.96; C, 51.09; H, 4.29; Found:, 4.95; C, 51.06; H, Br 4 -(6-Bromohexyl)phthalimide(8) A mixture of potassium phthalimide 5 (1.86g, 10 mmol) and 1,6-dibromohexane (12.2g, 50mmol) was stirred in dry DMF (10 ml) at 100 for 12 hours. The condenser was then set for distillation, and the excess of 1,6-dibromohexane and DMF were distilled off under reduced pressure. The crude product was purified by column chromatography (silica gel, ethyl acetate/light petroleum 1:40) to afford a colorless solid (2.5g, 81%). Mp C. 1 H MR (CDCl 3, 300MHz) (m, 2H), (m, 2H), 3.69 (t, 2H, J = 6.9 Hz), 3.40 (t, 2H, J = 6.9 Hz), (m, 4H), (m, 4H). 13 C MR (CDCl 3, 50MHz) , , , , 37.81, 33.70, 32.58, 28.40, 27.69, MS: (EI) 160 (100%), 309 (M + ) 22%, 311 (M + ) 19%. Elemental analysis calcd for C 14 H 16 Br 2 (310):, 4.52; C, 54.21; H, 5.20; Found:, 4.52; C, 54.14; H, (10-Bromodecyl)phthalimide (9) Br 6 3

4 A mixture of potassium phthalimide (5) (1.86 g, 10 mmol) and 1,10-dibromodecane (15 g, 50 mmol) was stirred in dry DMF (25ml) at 100 for 12 hours. The condenser was then set for distillation, and the excess of 1,10-dibromodecane and DMF were distilled off under reduced pressure. The crude product was purified by column chromatography (silica gel, ethyl acetate/light petroleum 1:40) to afford a colorless solid (3.25 g, 89%). Mp C. 1 H MR (CDCl 3, 300 MHz) (m, 2H), (m, 2H), 3.68 (t, 2H, J = 6.9 Hz), 3.40 (t, 2H, J = 6.9 Hz), (m, 4H), (m, 12H, CH 2 ). 13 C MR (CDCl 3, 50MHz) , , , , 38.02, 34.04, 32.79, 29.30, 29.08, 28.68, 28.55, 28.11, MS: (EI) 160 (100%), 365 (M + ) 25%, 367 (M + ) 23%. Elemental analysis calcd for C 18 H 24 Br 2 (366):, 3.82; C, 59.02; H, 6.60; Found:, 3.81; C, 59.05; H, ,6,7,10,11-Penta(hexyloxy- 2-(4-phthalimidobutyloxy)-triphenylene (10). Br 10 C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 4 A mixture of monhydroxypentahexyloxytriphenylene 3 (1.03 g, 1.38 mmol), -(4-bromobutyl)phthalimide 7 (0.51 g, 1.8 mmol), and potassium carbonate (1.52 g, 11 mmol) in DMF (13 ml) was heated under reflux for 48 hr. After cooling to room temperature, 60 ml of dichloromethane was added. The organic solution was washed with water (50mL) twice, and brine (20 ml) and dried over MgS 4. After the solvent was removed under reduced pressure, the resulting residue was purified by column chromatography (silica gel, ethyl acetate/light petroleum 1:30) to give 10 (1.18 g, 90%) as a pale yellow solid. Mp C. 1 H MR (CDCl 3, 300MHz) (m, 8H), (m, 2H), (m, 12H), (m, 2H), (m, 14H), (m, 10H), (m, 20H), (m, 15H). 13 C MR (CDCl 3, 75MHz) , , , , , , , , , , , , , , 69.60, 68.95, 37.68, 31.67, 29.39, 26.82, 25.82, 25.38, 22.64, IR (KBr) ν max (cm -1 ): 2928, 2857, 1771, 1707, 1618, 1518, 1468, 1437, 1396, 1327, 1261, 1175, 1047, 926, 893, 866, 837, 799, 768, 719, 667, 600, 528. HRMS (ESI): calcd. for C 60 H H ; found

5 3,6,7,10,11-Penta(hexyloxy)-2-(6-phthalimidohexyloxy)-triphenylene (11). C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 6 A mixture of monhydroxypentahexyloxytriphenylene 3 (0.75 g, 1.0 mmol), -(6-bromohexyl)phthalimide 8 (0.47 g, 1.5 mmol), and potassium carbonate (1.1 g, 5

6 8 mmol) in DMF (10 ml) was heated under reflux for 48 h. After cooling to room temperature, 60 ml of dichloromethane was added. The organic solution was washed with water (2 x 50mL), and brine (20 ml) and dried over MgS 4. After the solvent was removed under reduced pressure, the resulting residue was purified by column chromatography (silica gel, ethyl acetate/light petroleum 1:30) to give 11 (0.84 g, 87%) as a pale yellow solid. Mp C. 1 H MR (CDCl 3, 300MHz) (m, 8H), (m, 2H), (m, 12H), 3.73 (t, 2H, J = 6.9 Hz), (m, 12H), (m, 36H), (m, 15H). 13 C MR (CDCl 3, 75MHz) , , , , , , , 69.62, 37.84, 31.66, 29.38, 28.54, 26.63, 25.82, 22.64, 14.04; IR(KBr) ν max (cm -1 ): 2928, 2857, 1773, 1711, 1616, 1518, 1468, 1437, 1389, 1302, 1261, 1175, 1053, 922, 837, 793, 721, 600, 530. HRMS(ESI): calcd. for C 62 H H ; found

7 3,6,7,10,11-Penta(hexyloxy)-2-(10-phthalimidodecyloxy)-triphenylene (12). C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 C 6 H A mixture of monhydroxypentahexyloxytriphenylene 3 (0.97 g, 1.3 mmol), -(10-bromodecyl)phthalimide 9 (0.95 g, 2.6 mmol), and potassium carbonate (1.44 g, 10.4 mmol) in DMF (12 ml) was heated under reflux for 48 h. After cooling to room temperature, dichloromethane (60 ml) was added. The organic solution was washed with water (2 x 50 ml), brine (20 ml) and dried over MgS 4. After the solvent was removed under reduced pressure, the resulting residue was purified by column chromatography (silica gel, ethyl acetate/light petroleum 1:30) to give 12 (1.06 g, 91%) as a pale yellow solid. Mp C. 1 H MR (CDCl 3, 300 MHz) (m, 8H), (m, 2H), (m, 12H), 3.67 (t, 2H, J = 6.9 Hz), (m, 12H), (m, 44H), (m, 15H). 13 C MR (CDCl 3, 75 MHz) , , , , , , , 69.63, 38.02, 31.67, 29.39, 29.19, 28.58, 26.85, 25.83, 22.65, IR (KBr) ν max (cm -1 ): 2926, 2853, 1773, 1709, 1616, 1518, 1468, 1437, 1387, 1261, 1175, 1051, 1024, 924, 837, 797, 719, 600, 530. HRMS(ESI): calcd. for C 66 H H ; found

8 2-(4-Aminobutyloxy)-3,6,7,10,11-penta(hexyloxy)triphenylene (13) C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 H 2 Triphenylene 10 (0.92 g, 0.97 mmol) was dissolved in hot ethanol (30 ml), and aqueous hydrazine hydrate (3 ml, 85%) was added. The reaction mixture was heated under reflux for 1.5 h. After the mixture was cooled, water (20 ml) and DCM (60ml) were added. a 2 C 3 solution (10%) was added until the mixture was clear. The organic layer was washed with water and brine, dried (MgS 4 ) and concentrated. The crude material was purified by column chromatography (silica gel, DCM/Methanol 15:1), giving g (86%) as a colorless solid. 1 H MR (CDCl 3, 300MHz) 7.83 (br s, 6H), (m, 12H), 2.86 (t, 2H, J = 6.9 Hz), (m, 16H), (m, 30H), 0.94 (t, 15H, J = 6.9 Hz). 13 C MR (CDCl 3, 50MHz) , , , , , 69.58, 69.42, 69.31, 41.82, 31.62, 30.17, 29.35, 26.72, 25.78, 22.59, IR (KBr) νmax (cm-1): 3342, 3325, 2926, 2855, 1616, 1518, 1468, 1439, 1387, 1261, 1173, 1051, 1026, 926, 837, 799, 725, 600. HRMS(ESI): calcd. for C 52 H H ; found

9 2-(6-Aminohexyloxy)-3,6,7,10,11-penta(hexyloxy)triphenylene (14) C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 H 2 C 6 H

10 Prepared as above using triphenylene 11 (0.51 g, 0.52 mmol) to give g (80%) as a colorless solid. 1 H MR (CDCl 3, 300MHz) 7.83 (s, 6H), (m, 12H), 2.76 (br t, 2H), 2.52 (s, 2H), (m, 12H), (m, 36H), 0.94 (t, 15H, J = 6.9 Hz). 13 C MR (CDCl 3, 50MHz) , , , 69.60, 41.80, 32.96, 31.63, 29.37, 26.68, 25.97, 25.80, 22.61, IR (KBr) ν max (cm -1 ): 3442, 3325, 2928, 2855, 1616, 1518, 1468, 1439, 1387, 1261, 1173, 1049, 1026, 926, 837, 800, 725, 615, 600. HRMS (ESI): calcd. for C 54 H H ; found

11 2-(10-Aminodecyloxy)-3,6,7,10,11-penta(hexyloxy)triphenylene (15) C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 H 2 Prepared as above using triphenylene 12 (1.06 g, 1.03 mmol) giving 0.7 g (75%) of 15 as a colorless solid. 1 H MR (CDCl 3, 300MHz) 7.84 (s, 6H), (m, 12H), 2.67 (t, 2H, J = 6.9 Hz), (m, 12H), (m, 46H), 0.94 (t, 15H, J = 6.9 Hz). 13 C MR (CDCl 3, 50MHz) , , , 69.58, 42.13, 33.68, 31.62, 29.55, 29.46, 29.36, 26.84, 26.12, 25.80, 22.60, IR (KBr) ν max (cm -1 ): 3451, 3320, 2924, 2852, 1618, 1518, 1468, 1439, 1387, 1263, 1175, 1068, 1032, 837, 723. HRMS (ESI): calcd. for C 58 H H ; found

12 2-(2 -bromoethoxy)-3,6,7,10,11-penta(hexyloxy)triphenylene (16) C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 A mixture of monhydroxypentahexyloxytriphenylene 3 (1.49 g, 2.00 mmol), sodium hydroxide (0.16g, 4.00 mmol), tetrabutylammonium bromide (0.064 g, 0.2 mmol) and 1,2-dibromoethane (3.76 g, 20 mmol) were stirred in chloroform (10ml) and water (5ml) under 2 atmosphere at room temperature for 24 h. The organic layer was separated and methanol (40 ml) was added. The precipitate was filtered off and purified by column chromatography (silica, DCM/light petroleum 1:1) to afford 16 as a colorless solid (1.43g, 84%). Cr 48.3 Col h ( C) I. 1 H MR (CDCl 3, 300MHz) 7.92 (s, 1H), 7.82 (s, 4H), 7.81 (s, 1H), 4.54 (t, 2H, J = 6.6 Hz), 4.23 (t, 10H, J = 6.6 Hz), 3.77 (t, 2H, J = 6.6 Hz), (m, 10H), (m, 30H), 0.94 (t, 15H, J = 6.6 Hz). 13 C MR (CDCl 3, 50MHz) , , , , , , , , , , 70.25, 69.70, 69.50, 31.66, 29.46, 29.37, 25.83, 22.64, IR (KBr) ν max (cm -1 ): 2926, 2857, 1617, 1518, 1468, 1439, 1387, 1263, 1175, 1049, 926, 837, 799, 725, 648, 600. HRMS(ESI): calcd. for C 50 H 75 Br 6 +H ; found Br 12

13 3,6,7,10,11-Penta(hexyloxy)-2-(2-phthalimidoethyloxy)-triphenylene (17). C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 2 A mixture of 16 (1.04 g, 1.22 mmol) and potassium phthalimide 5 (0.45 g, 2.44 mmol) was stirred in dry DMF (10ml) at 100 for 36 h. The condenser was then set for 13

14 distillation, and the excess of 1,2-dibromoethane and DMF were distilled off under reduced pressure. The crude product was purified by column chromatography (silica gel, ethyl acetate/light petroleum 1:30) to afford 17 as a pale yellow solid (1.0g, 89%). Mp C. 1 H MR (CDCl 3, 300MHz) 8.00 (s, 1H), 7.93 (s, 1H), (m, 6H), (m, 2H), 4.50 (t, 2H, J = 6.6 Hz), 4.34 (t, 2H, J = 6.6 Hz), (m, 10H), (m, 10H), (m, 30H), 0.94 (t, 15H, J = 6.9 Hz). 13 C MR (CDCl 3, 75MHz) , , , , , , , , , , , , , , , , , , , , 69.77, 69.72, 69.56, 69.29, 66.05, 37.16, 31.67, 29.48, 29.40, 29.28, 25.83, 25.72, 22.65, IR (KBr) ν max (cm -1 ): 2926, 2855, 1774, 1711, 1616, 1518, 1468, 1437, 1395, 1261, 1175, 1049, 1024, 926, 837, 800, 714, 598, 530. HRMS (ESI): calcd. for C 58 H H ; found

15 2-(2-Aminoethyloxy)-3,6,7,10,11-penta(hexyloxy)triphenylene( 18) C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 C 6 H 13 H 2 Compound 17 (0.95 g, 1.03 mmol) was dissolved in hot ethanol (30 ml), and aqueous hydrazine hydrate (3 ml, 85%) was added. The reaction mixture was heated under reflux for 1.5 h. After the mixture was cooled, water (20 ml) and DCM (60ml) were added. a 2 C 3 solution (10%) was added until the mixture was clear. The organic layer was washed with water and brine, dried (MgS4) and concentrated. The crude material was purified by column chromatography (silica gel, DCM/methanol, 15:1), giving 18 (0.7 g, 85%) as a colorless solid. 1 H MR (CDCl 3, 300MHz) 7.80 (s, 2H), 7.79 (s, 1H), 7.78 (s, 1H), 7.74 (s, 1H), 7.66 (s, 1H), (m, 10H), 4.10 (t, 2H, J = 6.6 Hz), 3.25 (t, 2H, J = 6.6 Hz), 2.74 (s, 2H), (m, 10H), (m, 30H), (m, 15H). 13 C MR (CDCl 3, 50MHz) , , , , , , , , , , , , , 71.25, 69.63, 69.47, 41.47, 31.66, 31.59, 29.40, 29.30, 25.82, 22.61, IR (KBr) νmax (cm-1): 3435, 3325, 2928, 2857, 1618, 1518, 1437, 1387, 1261, 1175, 1068, 1049, 926, 837, 725, 600. HRMS (ESI): calcd. for C 50 H H ; found

16 PBITP 2 R R R R R R R R 2 2 R = (CH 2 ) 5 CH 3 2-(2-aminoethyloxy)-3,6,7,10,11-penta(hexyloxy)triphenylene (18) (0.6 g, 0.76 mmol) was dissolved in DMF (10 ml). 3,4:9,10-Perylenetetracarboxylic dianhydride 19 (0.18 g, mmol) and acetic acid (20 mg) were added to the solution and the mixture was heated to 85 C for 2 h under Ar. Then 0.15 g (0.38 mmol) of 19 was added and the reaction was maintained at 85 C for 24 h. The mixture was cooled to room temperature and of methanol (40 ml) was added. The precipitate was filtered off and purified by column chromatography (silica gel, DCM/methanol, 150:1), and recrystalliszed from chloroform and methanol to give PBITP 2 (0.48 g, 66%) as a dark red solid. Mp C. 1 H MR (CDCl 3, 300 MHz) 8.36 (d, 4H, J = 8.1 Hz), 7.99 (d, 4H, J = 8.1 Hz), 7.79 (s, 2H), 7.74 (s, 2H), 7.46 (s, 2H), 7.42 (s, 2H), 7.40 (s, 2H), 7.35 (s, 2H), 4.61 (s, 4H), 4.44 (s, 4H), 4.27 (t, 4H, J = 6.6 Hz), (m, 16H), (m, 20H), (m, 60H), (m, 30H). 13 C MR (CDCl 3, 50MHz) , , , , , , , , , , , , , , , , , , , , , 69.60, 69.33, 64.16, 38.71, 31.74, 31.63, 29.63, 29.50, 29.37, 26.08, 25.92, 25.87, 25.83, 22.69, 22.58, 14.14, 14.07, IR(KBr) ν max (cm -1 ): 2929, 2858, 1695, 1656, 1614, 1593, 1508, 1470, 1435, 1387, 1360, 1259, 1167, 1043, 926, R R 16

17 845, 806, 745, 646, 615, 588. HRMS(ESI): calcd. for C 124 H a ; found PBITP 4 R R R R R R 4 4 R R R = (CH R 2 ) 5 CH 3 R Prepared as above from 13 to give PBITP 4 (0.44 g, 68%) of as a dark red solid. Mp 17

18 C. 1 H MR (CDCl 3, 300 MHz) 8.17 (d, 4H, J = 8.1 Hz), 7.62 (d, 4H, J = 8.1 Hz), 7.34 (s, 2H), 7.23 (s, 2H), 7.19 (s, 2H), 7.08 (s, 2H), 7.05 (s, 2H), 6.90 (s, 2H), 4.37 (s, 4H), 4.18 (t, 8H, J = 6.6 Hz), 4.07 (t, 4H, J = 6.6 Hz), 3.98 (t, 4H, J = 6.6 Hz), 3.86 (t, 4H, J = 6.6 Hz), 3.77 (t, 4H, J = 6.6 Hz), (m, 8H), (m, 20H), (m, 60H), (m, 30H). 13 C MR (CDCl 3, 50MHz) , , , , , , , , , , , , , , , , , , 69.45, 69.05, 67.41, 40.04, 31.72, 31.69, 29.43, 29.31, 27.22, 25.93, 25.88, 25.84, 25.72, 23.23, 22.66, 14.11, IR(KBr) ν max (cm -1 ): 2931, 2858, 1695, 1660, 1616, 1595, 1508, 1472, 1437, 1385, 1342, 1263, 1171, 1040, 926, 837, 808, 746, 669, 629, 600. HRMS (ESI): calcd. for C 128 H H ; found

19 PBITP 6 R R R R R R R R 6 6 R = (CH 2 ) 5 CH 3 Prepared as above from 14 to give PBITP 6 (0.48 g, 66%) as a dark red solid. Mp C (from DSC). 1 H MR (CDCl 3, 300 MHz) 8.14 (d, 4H, J = 8.1 Hz), 7.65 (d, 4H, J = 8.1 Hz), 7.49 (s, 2H), 7.46 (s, 2H), 7.35 (s, 4H), 7.23 (s, 2H), 7.22 (s, 2H), (m, 12H), (m, 16H), (m, 28H), (m, 68H), (m, 30H). 13 C MR (CDCl 3, 50MHz) , , , , , , , , , , , , , , , , , , 69.52, 69.25, 40.18, 31.71, 29.43, 28.81, 27.49, 26.30, 26.08, 25.87, 22.67, IR(KBr) ν max (cm -1 ): 2931, 2858, 1695, 1660, 1616, 1593, 1508, 1470, 1437, 1385, 1343, 1262, 1170, 1039, 837, 808, 745, 646, 615, 588. HRMS (ESI): calcd. for C 132 H a ; found R R 19

20 PBITP 10 R R R R R R R R 10 R = (CH 2 ) 5 CH 3 Prepared as above from 15 to give PBITP 10 (0.49 g, 70%) as a dark red solid. 1 H MR (CDCl 3, 300 MHz) 8.07 (d, 4H, J = 8.1 Hz), 7.63 (d, 4H, J = 8.1 Hz), (m, 12H), (m, 28H), (m, 28H), (m, 84H), (m, 30H). 13 C MR (CDCl 3, 50MHz) , , , , , , , , , , , 69.29, 40.52, 31.69, 31.36, 29.37, 29.05, 28.88, 27.90, 26.99, 25.85, 22.65, IR(KBr) ν max (cm -1 ): 2928, 2857, 1693, 1659, 1616, 1593, 1558, 1508, 1470, 1437, 1385, 1344, 1261, 1169, 1038, 926, 837, 808, 746, 721, 667, 631, 600. HRMS (ESI): calcd. for C 140 H a ; found R R 20

21 21

22 Absorption and Fluorescence spectra for PBITP TPHx-C10-Pery 1.43uM 0.25 Absorption Wavelength /nm Fig. 1 the Uv-vis spectrum of PBITP 10, collected in DCM solution (1.43 um). ormalized Intensity (a.u) HAT6 1.5uM in dichloromethane, Wavelenhth / nm Fig. 2 The absorption spectrum of HAT6 ε = dm 3 mol -1 cm -1 22

23 50 40 PBITP uM in DCM Excition at 276nm Excition at 475nm Intensity (a.u) Wavelnegth / nm Fig. 3 The fluorescence spectrum of PBITP uM DCM solution PBITP10 monitored 580 nm monitored 610nm Intensity a.u Wavelength / nm Fig. 3 The fluorescence excitation spectra of PBITP