direct arylation of bodipy dyes-si tif · 2012-08-22 · s1 supporting information direct...
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Supporting Information Direct palladium-catalysed C–H arylation of BODIPY dyes at the 3- and 3,5-positions
Bram Verbelen, Volker Leen, Lina Wang, Noël Boens, Wim Dehaen*
Department of Chemistry, KU Leuven, Celestijnenlaan 200f – bus 02404, 3001 Leuven, Belgium. Fax: +32 16 327990; Tel: +32 16 327439; E-mail: [email protected]
Contents Experimental procedures and characterisation data ................................................................. S2
Optimisation of reaction protocol ........................................................................................ S2 General C–H arylation procedure......................................................................................... S3
NMR-spectra of new compounds ............................................................................................. S9 Spectroscopic data .................................................................................................................. S24
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Experimental procedures and characterisation data
Chemicals where purchased from Acros Organics and Sigma Aldrich, and used as received. All reactions were carried out in flame dried glassware, but no special precautions were taken for the exclusion of moisture. Solvents were not dried prior to use, except o-xylene which was dried over molecular sieves. All reactions were carried out under a nitrogen atmosphere.
1H and 13C NMR spectra were recorded at room temperature on a Bruker Avance 300 instrument operating at a frequency of 300 MHz for 1H and 75 MHz for 13C. In the case of ambiguous assignments, spectra were run on a Bruker 400 or Bruker 600. 1H NMR spectra in CDCl3 were referenced to tetramethylsilane (0.00 ppm) as an internal standard. 13C NMR spectra in CDCl3 were referenced to the CDCl3 (77.16 ppm) signal. Mass spectra were recorded on a Hewlett-Packard 5989A mass spectrometer (EI mode and CI mode). High-resolution mass data were obtained with a Kratos MS50TC instrument. Melting points were taken on a Reichert Thermovar and are uncorrected.
The electronic absorption spectra and absorbances were measured at 20 °C on a Perkin-Elmer Lambda 40 UV–vis spectrophotometer. Corrected steady-state excitation and emission spectra were recorded on a Spex Fluorolog instrument with temperature-controlled cell holder. Freshly prepared samples in 1 cm quartz cells were used to perform all UV–vis absorption and fluorescence measurements.
8-Arylated BODIPY dyes were prepared according to published literature procedures, through a water based dipyrromethane synthesis followed by oxidation and condensation.1 Optimisation of reaction protocol Table S1 Optimisation of the reaction protocol for the direct C–H arylation of 8-(2,6-dichlorophenyl)-BODIPY
Entry Reaction conditiona,b Yield / %c
Catalyst Ligand Additive Base Solvent PhX Temp Time 1 2a 3a
1 Pd(OAc)2 PPh3 / K2CO3 toluene PhBr-d5 110 °C 24 h 75 3 0
2 Pd(OAc)2 PPh3 / K2CO3 toluene PhBr-d5 110 °C 4 d 73 4 1
3 Pd(OAc)2 PPh3 PivOH K2CO3 toluene PhBr-d5 110 °C 24 h 59 15 3
4 Pd(OAc)2 PPh3 PivOH K2CO3 toluene PhBr-d5 110 °C 4 d 54 17 4
5 Pd(OAc)2 P(tBu)3HBF4 PivOH K2CO3 toluene PhBr-d5 110 °C 24 h 94 0 0
6d Pd(OAc)2 PCy3HBF4 PivOH K2CO3 toluene PhBr-d5 110 °C 24 h 33 45 19
7 Pd(OAc)2 DavePhos PivOH K2CO3 toluene PhBr-d5 110 °C 24 h 68 0 0
8 Pd2(dba)3 PCy3HBF4 PivOH K2CO3 toluene PhBr-d5 110 °C 24 h 22 37 21
9 Pd(TFA)2 PCy3HBF4 PivOH K2CO3 toluene PhBr-d5 110 °C 24 h 92 5 0
10 Pd(OAc)2 PCy3HBF4 PivOH Cs2CO3 toluene PhBr-d5 110 °C 24 h 32 19 14
11 Pd(OAc)2 PCy3HBF4 PivOH Na2CO3 toluene PhBr-d5 110 °C 24.5 h 92 5 1
12 Pd(OAc)2 PCy3HBF4 PivOH KOAc toluene PhBr-d5 110 °C 24 h 77 17 4
1 V. Leen, M. Van der Auweraer, N. Boens and W. Dehaen, Org. Lett., 2011, 13, 1470.
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13 Pd(OAc)2 PCy3HBF4 / CsOPiv toluene PhBr-d5 110 °C 24 h 69 23 6
14 Pd(OAc)2 PCy3HBF4 PivOH K2CO3 o-xylene PhBr-d5 110 °C 24 h 28 45 22
15 Pd(OAc)2 PCy3HBF4 PivOH K2CO3 o-xylene PhBr-d5 144 °C 24 h 22 41 26
16 Pd(OAc)2 PCy3HBF4 PivOH K2CO3 1,4-dioxane PhBr-d5 101 °C 24 h 56 30 9
17 Pd(OAc)2 PCy3HBF4 PivOH K2CO3 DMF PhBr-d5 110 °C 3.5 h 20 0 0 18 Pd(OAc)2 PCy3HBF4 PivOH K2CO3 DMF PhBr-d5 110 °C 24 h 0 0 0 19 Pd(OAc)2 PCy3HBF4 PivOH K2CO3 toluene PhCle 110 °C 4 d 94 2 0
20 Pd(OAc)2 PCy3HBF4 PivOH K2CO3 toluene PhIe 110 °C 4 d 90 4 0 a Experimental condition: 5 mol% catalyst, 10 mol% ligand, 30 mol% additive, 3 eq base, 1.1 eq arylhalide, solvent (0.1 M solution). b R is 2,6-dichlorophenyl. c All yields were determined via NMR-spectroscopy using pentadeuterated phenylhalides to avoid overlapping peaks. d Highest yielding condition. e No deuterated phenylhalide was used.
General C–H arylation procedure BODIPY 1 (one equivalent) was weighed together with K2CO3 (3 equivalents), Pd(OAc)2 (5 mol%), PCy3HBF4 (10 mol%), pivalic acid (30 mol%, IUPAC name 2,2-dimethylpropanoic acid)) and, if a solid, the bromoarene (1.1 equivalents). This was placed in a Schlenk flask with a magnetic stirring bar and dissolved in toluene (or o-xylene) to form a 0.1 M solution. Next, the reaction vessel was thrice evacuated and backfilled with nitrogen. If the bromoarene (1.1 equivalents) was a liquid it was added next, using a syringe. This reaction mixture was heated to 110 °C for the indicated time. Upon completion, the reaction mixture was cooled to room temperature. Subsequently, the solution was poured in diethyl ether (100 ml), washed three times with water (100 ml), dried over MgSO4, filtered, and evaporated to dryness. The crude product was purified chromatographically. 3-Phenyl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 2a
The compound was prepared following the general procedure using 0.4 mmol 8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene in o-xylene for 24 h. Bromobenzene was the bromoarene used. The crude product was purified via column chromatography (silica; petroleum ether/CH2Cl2; 2:1 v/v) providing the desired product 2a in 44% (73 mg) and the diarylated product 3a in 17% (34 mg) yield. 2a: Red crystals with a green lustre; Mp 278 °C; 1H-NMR (CDCl3, 300 MHz): δ 8.06-7.95 (m, 2H), 7.85 (s, 1H), 7.56-7.39 (m, 6H), 6.75 (d, 1H, J = 3.96 Hz), 6.68 (d, 1H, J = 3.96 Hz), 6.62 (d, 1H, J = 3.00 Hz), 6.49 (s, 1H) ppm; 13C-NMR (CDCl3, 75 MHz): δ 161.8, 143.4, 135.6, 132.0, 131.8, 131.3, 131.1, 130.5, 129.8, 129.7, 129.6, 129.5, 128.5, 128.4, 128.1, 121.8, 118.6 ppm; MS (EI): 412; HRMS: Calculated for C21H13BCl2F2N2: 412.05169, found 412.05171. 3a: Purple crystals with a copper lustre; Mp 140 °C; 1H-NMR (CDCl3, 300 MHz): δ 7.96-7.86 (m, 4H), 7.54-7.37 (m, 9H), 6.66 (d, 2H, J = 4.14 Hz), 6.61 (d, 2H, J = 4.14 Hz) ppm; 13C-NMR (CDCl3, 75 MHz): δ 159.9, 135.8, 132.5, 132.2, 131.2, 129.9, 129.7, 129.7, 129.6,
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129.2, 128.4, 128.3, 121.6 ppm; MS (EI): 488; HRMS: Calculated for C27H17BCl2F2N2: 488.08299, found 488.08194. 3-p-Anisyl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 2b
The compound was prepared following the general procedure using 0.4 mmol 8-(2,6-dichloropheny)l-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene in toluene for 43 h. 4-Bromoanisole was the bromoarene used. The crude product was purified via column chromatography (silica; petroleum ether/diethyl ether; 2:1 v/v) providing the desired product 2b in 42% (74 mg) and the diarylated product 3b in 10% (21 mg) yield. 2b: Dark red crystals with a copper lustre; Mp 70 °C; 1H-NMR (CDCl3, 300 MHz): δ 8.04 (d, 2H, J = 8.85 Hz), 7.80 (s, 1H), 7.52-7.37 (m, 3H), 7.02 (d, 2H, J = 8.85 Hz), 6.76-6.69 (m, 2H), 6.56 (s, 1H), 6.46 (s, 1H), 3.89 (s, 3H) ppm; 13C-NMR (CDCl3, 75 MHz): δ 162.1, 161.8, 141.9, 137.5, 135.7, 132.0, 131.8, 131.7, 131.7, 131.4, 131.2, 128.3, 126.8, 124.2, 121.9, 118.0, 114.2, 55.5 ppm; MS (EI): 442; HRMS: Calculated for C22H15BCl2F2N2O: 442.06226, found 442.06248. 3b: Purple crystals with a green lustre; Mp 63 °C; 1H-NMR (CDCl3, 300 MHz): δ 7.93 (d, 4H, J = 8.85 Hz), 7.52-7.38 (m, 3H), 6.97 (d, 4H, J = 8.85 Hz), 6.60 (s, 4H), 3.86 (s, 6H) ppm; 13C-NMR (CDCl3, 75 MHz): δ 160.9, 159.1, 135.8, 132.2, 131.3, 131.3, 131.2, 130.9, 128.5, 128.2, 125.0, 120.9, 113.8, 55.3 ppm; MS (EI): 548; HRMS: Calculated for C29H21BCl2F2N2O2: 548.10412, found 548.10536. 3-Thien-3-yl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 2d
The compound was prepared following the general procedure using 0.1 mmol 8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene in toluene for 27 h. 3-Bromothiophene was the bromoarene used. The crude product was purified via column chromatography (silica; petroleum ether/CH2Cl2; 2:1 v/v) providing the desired product 2d in 55% (23 mg) and the diarylated product 3d in 10% (5 mg) yield. 2d: Dark purple crystals with a green lustre; Mp 214 °C; 1H-NMR (CDCl3, 300 MHz): δ 8.44 (d, 1H, J = 1.53 Hz), 7.84 (s, 1H), 7.72 (d, 1H, J = 4.71 Hz), 7.53-7.35 (m, 4H), 6.80 (d, 1H, J = 4.32 Hz), 6.72 (d, 1H, J = 4.32 Hz), 6.58 (d, 1H, J = 3.39 Hz), 6.49 (s, 1H) ppm; 13C-NMR (CDCl3, 75 MHz): δ 155.7, 142.4, 137.2, 135.6, 133.6, 132.1, 131.9, 131.3, 131.2,
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130.6, 130.5, 128.9, 128.4, 127.1, 125.9, 121.8, 118.3 ppm; MS (EI): 418; HRMS: Calculated for C19H11BCl2F2N2S: 418.00811, found 418.00869. 3d: Blue solid; Mp 205 °C; 1H-NMR (CDCl3, 300 MHz): δ 8.37 (s, 2H), 7.69 (d, 2H, J = 4.71 Hz), 7.52-7.33 (m, 5H), 6.75 (d, 2H, J = 3.78 Hz), 6.59 (d, 2H, J = 3.78 Hz) ppm; 13C-NMR (CDCl3, 75 MHz): δ 153.2, 136.0, 135.9, 132.7, 131.1, 129.3, 129.2, 129.0, 129.0, 128.6, 128.3, 125.6, 121.1 ppm; MS (EI): 500; HRMS: Calculated for C23H13BCl2F2N2S2: 499.99583, found 499.99666. 3-Mesityl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 2e
The compound was prepared following the general procedure using 0.1 mmol 8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene in toluene for 43 h. 2-Bromo-1,3,5-trimethylbenzene was the bromoarene used. The crude product was purified via column chromatography (silica; petroleum ether/CH2Cl2; 1:1 v/v) providing the desired product 2e in 35% (16 mg) yield. Orange solid with a green lustre; Mp 152 °C; 1H-NMR (CDCl3, 300 MHz): δ 7.72 (s, 1H), 7.55-7.39 (m, 3H), 6.96 (s, 2H), 6.79 (d, 1H, J = 4.14 Hz), 6.62 (d, 1H, J = 4.14 Hz), 6.44 (d, 1H, J = 3.75 Hz), 6.37 (d, 1H, J = 4.14 Hz), 2.34 (s, 3H), 2.17 (s, 6H) ppm; 13C-NMR (CDCl3, 75 MHz): δ 162.3, 143.6, 139.2, 139.1, 137.4, 135.7, 135.5, 131.8, 131.3, 131.1, 130.8, 129.1, 129.0, 128.4, 127.8, 121.7, 118.4, 21.4, 20.1 ppm; MS (EI): 454 (M), 434 (M-HF); HRMS: Calculated for C24H19BCl2F2N2: 454.09864, found 454.09852. 3-(1-Naphthyl)-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 2f
The compound was prepared following the general procedure using 0.4 mmol 8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene in o-xylene for 24 h. 1-Bromonaphthalene was the bromoarene used. The crude product was purified via column chromatography (silica; petroleum ether/CH2Cl2; 2:1 v/v) providing the diarylated product 3f in 16% (37 mg) yield and impure 2f. Analytically pure 2f was obtained through HPLC purification (silica; toluene/CH2Cl2; 2:1 v/v), providing the desired product 2f in 20% (37 mg) yield. 2f: Red crystals with a green lustre; Mp 282 °C; 1H-NMR (CDCl3, 300 MHz): δ 8.03-7.95 (m, 2H), 7.94-7.84 (m, 2H), 7.77 (s, 1H), 7.62 (t, 1H, J = 7.73 Hz), 7.55-7.43 (m, 5H), 6.83 (d, 1H, J = 4.14 Hz), 6.65 (m, 2H), 6.46 (d, 1H, J = 3.03 Hz) ppm; 13C-NMR (CDCl3, 75 MHz): δ 160.1, 144.0, 139.3, 136.1, 135.6, 134.2, 133.6, 131.9, 131.8, 131.3, 130.3, 130.0,
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129.8, 128.6, 128.4, 126.7, 126.2, 126.1, 125.0, 123.4, 118.8 ppm; MS (EI): 462; HRMS: Calculated for C25H15BCl2F2N2: 462.06734, found 462.06839. 3f: Purple solid with a copper lustre; Mp: decomposition at 310 °C; 1H-NMR (CDCl3, 300 MHz): δ 7.91-7.77 (m, 8H), 7.60-7.54 (m, 2H), 7.52-7.37 (m, 7H), 6.79 (d, 2H, J = 3.21 Hz), 6.59 (d, 2H, J = 3.39 Hz) ppm; 13C-NMR: product is too insoluble to obtain a fully resolved spectrum; MS (EI): 588; HRMS: Calculated for C35H21BCl2F2N2: 588.11429, found 588.11553. 3,8-Diphenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 2i
The compound was prepared following the general procedure using 0.2 mmol 8-phenyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene in o-xylene for 28 h. Bromobenzene was the bromoarene used. The crude product was purified via column chromatography (silica; petroleum ether/CH2Cl2; 2:1 v/v) providing the desired product 2i in 31% (21 mg) and the diarylated product 3i in 32% (27 mg) yield. 2i: Red solid with a green lustre; Mp 58 °C; 1H-NMR (CDCl3, 300 MHz): δ 8.00-7.92 (m, 2H), 7.85 (s, 1H), 7.63-7.45 (m, 8H), 6.99 (d, 1H, J = 4.17 Hz), 6.86 (d, 1H, J = 3.60 Hz), 6.69 (d, 1H, J = 4.35 Hz), 6.52 (d, 1H, J = 2.46 Hz) ppm; 13C-NMR (CDCl3, 100 MHz): δ 160.6, 145.8, 142.5, 137.3, 134.3, 132.9, 132.3, 130.7, 130.6, 130.1, 129.8, 129.6, 128.5, 128.5, 125.9, 121.1, 118.2 ppm; MS (EI): 344; HRMS: Calculated for C21H15BF2N2: 344.12964, found 344.13011. 3i: Dark purple solid; Mp 191 °C; 1H-NMR (CDCl3, 300 MHz): δ 7.91-7.83 (m, 4H), 7.63-7.50 (m, 5H), 7.47-7.37 (m, 6H), 6.90 (d, 2H, J = 4.35 Hz), 6.63 (d, 2H, J = 4.17 Hz) ppm; 13C-NMR (CDCl3, 75 MHz): δ 159.0, 144.2, 136.5, 134.4, 132.7, 131.0, 130.7, 130.2, 129.6, 128.4, 128.3, 121.0 ppm (one carbon overlap); MS (EI): 420; HRMS: Calculated for C27H19BF2N2: 420.16094, found 420.16196. 3-Phenyl-8-(p-nitrophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 2j
The compound was prepared following the general procedure using 0.2 mmol 8-(p-nitrophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene in o-xylene for 46 h. Bromobenzene was the bromoarene used. The crude product was purified via column chromatography (silica; petroleum ether/CH2Cl2; 1:1 v/v) providing the desired product 2j in 28% (22 mg) and the diarylated product 3j in 18% (17 mg) yield.
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2j: Purple crystals with a green lustre; Mp 193 °C; 1H-NMR (CDCl3, 300 MHz): δ 8.41 (d, 2H, J = 8.85 Hz), 8.00-7.93 (m, 2H), 7.89 (s, 1H), 7.77 (d, 2H, 8.67 Hz), 7.55-7.47 (m, 3H), 6.89 (d, 1H, J = 4.53 Hz), 6.79-6.70 (m, 2H), 6.55 (d, 1H, J = 3.21 Hz) ppm; 13C-NMR (CDCl3, 75 MHz): δ 149.1, 143.5, 140.4, 136.9, 133.7, 132.4, 131.8, 131.5, 130.6, 129.7, 129.6, 129.6, 129.2, 128.6, 123.8, 122.1, 118.9 ppm; MS (EI): 389; HRMS: Calculated for C21H14BF2N3O2: 389.11471, found 389.11459. 3j: Dark purple solid; Mp 99 °C; 1H-NMR (CDCl3, 300 MHz): δ 8.42 (d, 2H, J = 8.67 Hz), 7.92-7.83 (m, 4H), 7.79 (d, 2H, J = 8.46 Hz), 7.49-7.39 (m, 6H), 6.79 (d, 2H, J = 4.14 Hz), 6.67 (d, 2H, J = 3.96 Hz) ppm; 13C-NMR (CDCl3, 75 MHz): δ 160.3, 140.8, 136.0, 132.3, 131.6, 130.4, 130.1, 129.7, 129.6, 129.6, 128.5, 123.7, 121.8 ppm; MS (EI): 465; HRMS: Calculated for C27H18BF2N3O2: 465.14601, found 465.14769. 3-Phenyl-5-thien-3-yl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 4
The compound was prepared following the general procedure using 0.2 mmol 3-phenyl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 2a in o-xylene for 48 h. 3-Bromothiophene was the bromoarene used. The crude product was purified via column chromatography (silica; petroleum ether/CH2Cl2; 3:1 v/v) providing the desired product in 62% (61 mg) yield. Dark purple solid; Mp 197 °C; 1H-NMR (CDCl3, 300 MHz): δ 8.32 (s, 1H), 7.97 (d, 2H, J = 6.03 Hz), 7.65 (d, 1H, J = 4.71 Hz), 7.54-7.39 (m, 6H), 7.38-7.31 (m, 1H), 6.75 (d, 1H, J = 3.93 Hz), 6.68-6.58 (m, 3H) ppm; 13C-NMR (CDCl3, 75 MHz): δ 159.0, 154.0, 136.2, 135.9, 132.8, 132.4, 132.2, 131.1, 129.7, 129.7, 129.4, 129.0, 128.4, 128.3, 125.6, 121.4, 121.2 ppm; MS (EI): 494; HRMS: Calculated for C25H15BCl2F2N2S: 494.03941, found 494.04022. 1,4-Di(3-phenyl-5-yl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)benzene 5
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The compound was prepared following the general C–H arylation procedure using 0.36 mmol 3-phenyl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 2a in toluene for 53 h. 1,4-Dibromobenzene (0.15 mmol, 0.42 equivalents) was used as bromoarene. The crude product was purified via column chromatography (silica; petroleum ether/ diethyl ether; 1:1 v/v) providing the desired product 5 in 23% (31 mg) yield. Dark crystals; Mp: decomposition at 290 °C; 1H-NMR (CDCl3, 300 MHz): δ 8.02 (s, 4H), 7.93 (d, 4H, J = 5.85 Hz), 7.55-7.38 (m, 12 H), 6.71 (s, 2H), 6.67 (s, 4H), 6.63 (s, 2H) ppm; 13C-NMR (CDCl3, 150 MHz): δ 160.2, 158.9, 137.1, 136.5, 136.3, 135.9, 133.4, 132.5, 132.1, 131.2, 129.9, 129.7, 129.2, 129.2, 128.4, 128.3, 121.9, 121.7 ppm (two carbons overlap); MS (ESI): 923 (M+ + Na+), 1823 (M+ + M+ + Na+).
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NMR-spectra of new compounds 2a, 1H, 300 MHz, CDCl3
2.0105
1.0000
6.1054
0.9983
1.0419
0.9684
0.9987
Integral
8.0065
7.9920
7.8451
7.5050
7.4861
7.4485
7.4271
7.3970
6.7530
6.7398
6.6890
6.6758
6.6287
6.6187
6.4894
(ppm)
0.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
2a, 13C, 75 MHz, CDCl3
161.7851
143.3516
135.5732
131.9730
131.8203
131.2748
131.1257
130.4639
129.7620
129.7075
129.6493
129.5947
128.5292
128.3620
128.0601
121.8017
118.6416
(ppm)
0102030405060708090100110120130140150160170180
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3a, 1H, 300 MHz, CDCl3
4.0000
9.0331
1.9045
2.0056
Integral
7.9249
7.9167
7.8985
7.5206
7.4962
7.4510
7.4328
7.4171
6.6695
6.6557
6.6143
6.6005
(ppm)
0.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
3a, 13C, 75 MHz, CDCl3
159.9341
135.8386
132.5258
132.1585
131.1657
129.8711
129.7147
129.6602
129.6093
129.1656
128.4020
128.3474
121.5653
(ppm)
102030405060708090100110120130140150160170
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2b, 1H, 300 MHz, CDCl3
2.0512
1.0000
3.1274
2.0161
2.0308
1.0021
1.0461
3.0711
Integral
8.0516
8.0221
7.7981
7.5031
7.4955
7.4729
7.4359
7.4146
7.4045
7.3832
7.0386
7.0091
6.7379
6.7235
6.7078
6.6934
6.5666
6.5547
6.4605
3.8921
(ppm)
0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
2b, 13C, 75 MHz, CDCl3
162.1051
161.7851
141.8607
137.5078
135.6604
131.9839
131.7912
131.7294
131.6675
131.4166
131.1621
128.3329
126.8383
124.2418
121.9363
117.9688
114.1614
55.5483
(ppm)
0102030405060708090100110120130140150160170
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3b, 1H, 300 MHz, CDCl3
4.0124
3.1768
4.0312
3.9195
6.0000
Integral
7.9431
7.9136
7.5131
7.5075
7.4842
7.4378
7.4158
7.4070
7.3851
6.9809
6.9514
6.6011
3.8614
(ppm)
0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.4
3b, 13C, 75 MHz, CDCl3
160.8882
159.0518
135.8036
132.2326
131.3053
131.2507
131.1926
130.8580
128.4579
128.1488
124.9850
120.9340
113.8319
55.2951
(ppm)
0102030405060708090100110120130140150160170
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S13
2d, 1H, 300 MHz, CDCl3
0.9522
1.0000
0.9994
4.1060
0.9905
0.9875
0.9779
1.0065
Integral
8.4446
8.4395
7.8370
7.7246
7.7089
7.5012
7.4943
7.4723
7.4372
7.4158
7.4058
7.3895
6.8051
6.7907
6.7254
6.7110
6.5823
6.5710
6.4863
(ppm)
0.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
2d, 13C, 75 MHz, CDCl3
155.7194
142.3880
137.2314
135.6422
133.6203
132.1512
131.9148
131.3039
131.2166
130.6348
130.5293
128.9256
128.3547
127.1183
125.9364
121.7763
118.2743
(ppm)
0102030405060708090100110120130140150160170
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S14
3d, 1H, 300 MHz, CDCl3
1.7592
2.0826
5.6113
2.0000
1.9378
Integral
8.3667
7.6970
7.6813
7.4905
7.4667
7.4240
7.3719
6.7518
6.7392
6.5999
6.5873
(ppm)
0.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
3d, 13C, 75 MHz, CDCl3
153.1920
136.0095
135.8968
132.6530
131.0784
129.2820
129.1729
129.0383
128.9947
128.6165
128.3147
125.5691
121.0817
(ppm)
102030405060708090100110120130140150160170
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S15
2e, 1H, 300 MHz, CDCl3
1.0377
3.2144
1.9802
0.9434
0.9521
0.9785
0.9574
2.9562
6.0000
Integral
7.7214
7.5432
7.5206
7.5130
7.4898
7.4534
7.4321
7.4220
7.4007
6.9594
6.7956
6.7818
6.6268
6.6130
6.4441
6.4316
6.3776
6.3638
2.3398
2.1723
(ppm)
0.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
2e, 13C, 75 MHz, CDCl3
162.2942
143.5516
139.2315
139.1442
137.3732
135.6750
135.4786
131.7621
131.2821
131.0603
130.7657
129.1220
128.9947
128.3620
127.7983
121.7108
118.4307
21.4415
20.1433
(ppm)
102030405060708090100110120130140150160170
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S16
2f, 1H, 300 MHz, CDCl3
2.0511
2.1174
1.0000
1.1356
5.3321
0.9494
1.8840
0.9409
Integral
7.9958
7.9776
7.9669
7.9336
7.9054
7.8809
7.8552
7.7679
7.6412
7.6154
7.5897
7.5338
7.4968
7.4874
7.4679
7.4453
7.4146
6.8327
6.8189
6.6676
6.6538
6.6394
6.4643
6.4542
(ppm)
0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
2f, 13C, 75 MHz, CDCl3
160.0977
143.9662
139.3369
136.0495
135.5586
134.2167
133.5767
131.9294
131.7694
131.3439
130.3329
129.9802
129.8093
128.6492
128.4056
126.7401
126.2091
126.0564
125.0382
123.3909
118.7507
(ppm)
102030405060708090100110120130140150160170
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S17
3f, 1H, 300 MHz, CDCl3
8.1766
2.1529
7.5502
2.0000
2.0318
Integral
7.8489
7.8213
7.5872
7.5621
7.5050
7.4748
7.4321
6.7907
6.7800
6.5967
6.5854
(ppm)
0.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S18
2i, 1H, 300 MHz, CDCl3
2.0340
1.0000
8.1964
0.9814
0.9581
0.9649
0.9673
Integral
7.9757
7.9669
7.9500
7.8470
7.6004
7.5903
7.5771
7.5558
7.5363
7.5043
7.4861
6.9922
6.9783
6.8679
6.8559
6.6972
6.6827
6.5252
6.5170
(ppm)
0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
2i, 13C, 100 MHz, CDCl3
160.5941
145.7709
142.4826
137.3422
134.2872
132.9018
132.3404
130.6707
130.5613
130.1311
129.8395
129.5916
128.5052
128.4833
125.9314
121.1483
118.2245
(ppm)
102030405060708090100110120130140150160170
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S19
3i, 1H, 300 MHz, CDCl3
4.0000
5.3312
6.1188
1.9591
1.9889
Integral
7.9114
7.8931
7.6009
7.5795
7.5521
7.5339
7.4425
7.4273
6.9037
6.8915
6.6419
6.6297
(ppm)
0.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
3i, 13C, 75 MHz, CDCl3
158.9801
144.2062
136.4689
134.4280
132.7221
131.0163
130.6508
130.2243
129.5846
128.3661
128.3052
121.0249
(ppm)
102030405060708090100110120130140150160170
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S20
2j, 1H, 300 MHz, CDCl3
1.9470
2.0510
1.0467
2.0147
3.0355
0.9289
2.0000
1.0157
Integral
8.4270
8.3975
7.9851
7.9726
7.9606
7.9531
7.8885
7.7868
7.7579
7.5219
7.5087
7.4999
6.8930
6.8779
6.7637
6.7505
6.7361
6.5597
6.5490
(ppm)
0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
2j, 13C, 75 MHz, CDCl3
149.1191
143.5371
140.4170
136.9368
133.7294
132.3767
131.8203
131.4603
130.6311
129.7002
129.6493
129.5947
129.2384
128.6129
123.7618
122.1145
118.9216
(ppm)
0102030405060708090100110120130140150160170
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S21
3j, 1H, 300 MHz, CDCl3
1.8910
4.0178
1.9695
6.2012
1.8756
2.0000
Integral
8.4364
8.4075
7.8941
7.8815
7.8696
7.8627
7.8062
7.7774
7.4642
7.4491
7.4378
7.4303
6.7995
6.7857
6.6796
6.6658
(ppm)
0.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
3j, 13C, 75 MHz, CDCl3
160.2650
140.8352
135.9986
132.3476
131.5584
130.4202
130.0566
129.6711
129.6166
129.5656
128.4820
123.7072
121.8417
(ppm)
0102030405060708090100110120130140150160170
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S22
4, 1H, 300 MHz, CDCl3
0.9296
1.9932
0.9746
6.2591
1.0747
0.9761
3.0000
Integral
8.3240
7.9826
7.9625
7.6587
7.6430
7.5144
7.4899
7.4667
7.4510
7.4284
7.3976
7.3556
7.3462
6.7649
6.7518
6.6532
6.6212
(ppm)
0.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.48.8
4, 13C, 75 MHz, CDCl3
159.0104
154.0066
136.1914
135.8641
132.7621
132.4203
132.1839
131.1257
129.7475
129.7002
129.4056
128.9874
128.4056
128.3329
125.6055
121.4126
121.2090
(ppm)
5101520253035404550556065707580859095100105110115120125130135140145150155160165170175
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S23
5, 1H, 300 MHz, CDCl3
4.0000
4.0249
12.243
2.0154
3.8436
2.0330
Integral
8.0221
7.9418
7.9223
7.5257
7.5018
7.4547
7.4340
6.7147
6.6702
6.6306
(ppm)
0.00.40.81.21.62.02.42.83.23.64.04.44.85.25.66.06.46.87.27.68.08.4
5, 13C, 150 MHz, CDCl3
160.1510
158.8603
137.1081
136.4737
136.2768
135.8612
133.4183
132.4995
132.1422
131.1797
129.9473
129.6848
129.2473
129.1525
128.4233
128.3430
121.8896
121.7073
(ppm)
102030405060708090100110120130140150160170
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S24
Spectroscopic data
Figure S1 (a) Normalized, visible absorption spectra of a selection of meso-(2,6-dichlorophenyl) substituted BODIPY dyes (1, 2d, 2f, 3d, 4) in THF. (b) Corresponding normalized fluorescence emission spectra. Note that merging figures (a) and (b) produces the ‘congested’ Figure 1.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012
S25
Table S2 Spectroscopic and fluorescence quantum yield data of bis-BODIPY 5 as a function of solvent. The solvents are listed from top to bottom according to increasing refractive index n.
Product Solvent λabs(max) a
/ nm λem(max) b
/ nm ν∆ c
/ cm-1
Φ d
5
MeOH 621 707 1959 e
MeCN 612 707 2196 e
Ethyl acetate 625 708 1876 0.58 ± 0.01 THF 636 717 1776 0.524 ± 0.003 Toluene 638 718 1746 0.634 ± 0.004
a Absorption maximum. b Fluorescence emission maximum. c Stokes shift (=1/λabs(max) – 1/λem(max)). d Fluorescence quantum yield ± one standard uncertainty. Φ determined vs. cresyl violet in methanol (Φr = 0.55) as reference.
e Not possible to obtain reliable Φ values due to very limited solubility in the solvents indicated.
Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012