LETTER
Highly Colored BODIPY Dyes
1471
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and references cited therein.
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Chem. Soc. 2012, 134, 17404.
Figure 6 Steady state emission using a PMT liquid-nitrogen-cooled
near-infrared detector for dyes: 13 (red trace), 16 (green trace) and 17
(blue trace).
(13) Bura, T.; Retailleau, P.; Ziessel, R. Angew. Chem. Int. Ed.
2010, 49, 6659.
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B 2010, 114, 4461.
one case, this new approach to the synthesis has provided
a dye bearing polyaromatic modules on the boron center.
Multiple cascade energy transfer events have been ex-
ploited to channel excitonic energy to a single emitting
dye lying at low energy. This concept could certainly be
extended to provide dyes emitting above 1000 nm. The
present systems confirm that the construction of a module
offering orthogonal functionalization is suitable to ensure
regioselectivity during the cross-coupling or Knoevenagel
reactions and that the introduction of paraffin chains en-
genders solubility in a wide variety of solvents. The legit-
imate prospect for the use of these new materials as
luminescent molecular light concentrators in bulk hetero-
junctions for solar energy conversion is currently under
development.29,30
(16) Ziessel, R.; Bura, T.; Olivier, J.-H. Synlett 2010, 2304.
(17) Preparation of Compound 13: To a solution of BODIPY
12 (207.9 mg, 0.46 mmol) in toluene (70 mL) were added 6-
[4-(diphenylamino)phenyl]-4,4-dihexyl-4H-cyclopenta[2,1-
b:3,4-b′]dithiophene-2-carbaldehyde (11; 856.3 mg, 1.39
mmol), piperidine (1 mL) and p-toluenesulfonic acid (p-
TsOH). The resulting mixture was stirred at reflux and the
solvent was distilled to dryness using a Dean–Starck
apparatus. Afterwards, the organic product was extracted
with CH2Cl2, washed with H2O and brine. The organic layer
was dried over anhyd MgSO4 and evaporated under vacuum.
The crude product was purified by silica gel chromatography
(from 80:20 → 50:50 petroleum ether–CH2Cl2) and
recrystallized by evaporation in CH2Cl2–EtOH and washed
with pentane to afford a deep-brown red compound (745.8
mg, 98%). 1H NMR (400 MHz, CD2Cl2): δ = 7.88 (d, 3J = 8.1
Hz, 2 H), 7.52 (d, 3J = 8.5 Hz, 4 H), 7.42 (s, 4 H), 7.29 (t, 3J
= 7.9 Hz, 8 H), 7.17 (d, 4J = 4.0 Hz, 4 H), 7.15 (d, 3J = 8.4
Hz, 2 H), 7.12 (d, 3J = 7.7 Hz, 8 H), 7.02–7.08 (m, 8 H), 6.65
(s, 2 H), 1.88–1.96 (m, 8 H), 1.50 (s, 6 H), 1.13–1.24 (m, 24
H), 0.95–1.05 (m, 8 H), 0.81 (t, 3J = 6.7 Hz, 12 H). 13C NMR
(101 MHz, CD2Cl2): δ = 161.4, 159.5, 152.3, 148.0, 147.8,
146.9, 143.5, 141.8, 140.6, 138.8, 135.7, 135.5, 135.1,
134.1, 131.5, 130.4, 129.9, 129.6, 126.6, 125.1, 124.2,
123.8, 123.3, 118.5, 117.6, 116.2, 95.2, 38.6, 34.7, 32.2,
30.3, 25.1, 23.2, 22.9, 15.3, 14.4. MS (EI): m/z (%) = 1649.5
(100.0), 1629.5 (30). Anal. Calcd for C99H100BF2IN4S4: C,
72.07; H, 6.11; N, 3.40. Found: C, 71.85; H, 5.80; N, 3.11.
(18) (a) Harriman, A.; Mallon, L. J.; Goeb, S.; Ziessel, R. Phys.
Chem. Chem. Phys. 2007, 9, 5199. (b) Harriman, A.;
Mallon, L. J.; Goeb, S.; Ulrich, G.; Ziessel, R. Chem. Eur. J.
2009, 15, 4553.
Acknowledgment
We thank the Centre National de la Recherche Scientifique (CNRS)
for financial support of this work. Professor Jack Harrowfield (ISIS
in Strasbourg) is warmly acknowledged for commenting this manu-
script prior to publication.
Supporting Information for this article is available online
at
10.1055/s-00000083.SunpfgIpi
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References and Notes
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(21) Preparation of Compound 16: To a degassed solution of 13
(63 mg, 0.038 mmol) and 15 (22 mg, 0.046 mmol) in
benzene (10 mL) and Et3N (2 mL) was added [Pd(PPh3)4]
(10 mg). The resulting mixture was stirred for 19 h at 70 °C
and then cooled to r.t. After evaporation of the solvent under
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