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

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

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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,


S6

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


S8

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+).


S9

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


S10

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


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


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)

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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)

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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)

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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


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)

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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)

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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


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


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


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


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.


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.


Direct arylation of BODIPY dyes-SI tif · 2012-08-22 · S1 Supporting Information Direct...

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