BODIPY-Based NIR Cyanine-Like Dyes
= 13.6, 14.4, 28.1, 30.5, 47.8, 58.6, 59.8, 61.5, 123.1, 125.9, 127.5, was filtered and refluxed in EtOAc. The crude product was filtered
128.1, 128.5, 128.9, 129.6, 130.6, 130.7, 140.7, 143.9, 144.6, 155.2,
164.2, 165.3 ppm. LC-MS: m/z = 702 [M + H]+. C42H41BF2N3O4
(700.61): calcd. C 72.00, H 5.90, N 6.00; found C 72.17, H 5.74, N
6.10.
and recrystallized from CH3CN; yield 0.04 g (10%); m.p. Ͼ250 °C.
1H NMR (300 MHz, [D6]CDCl3): δ = 1.03 (t, J = 4.7 Hz, 6 H,
CH3CH2), 1.37 (t, J = 4.4 Hz, 6 H, CH3CH2), 3.92 (q, J = 4.4 Hz,
4 H, CH3CH2), 4.18 (q, J = 4 Hz, 4 H, CH3CH2), 5.89 (d, J =
7.1 Hz, 2 H, CH), 6.57 (s, 1 H, CH), 6.89–7.31 (m, 20 H), 7.67 (t,
J = 7.9 Hz, 2 H, CH) ppm. C51H46BF2N4O4S2: calcd. C 68.68, H
5.20, N 6.28; found C 68.81, H 5.39, N 6.50.
Diethyl 3-[3-(3-Ethyl-3H-benzothiazol-2-ylidene)propen-1-yl]-4,4-di-
fluoro-5-methyl-1,7-diphenyl-4-bora-3a,4a-diaza-s-indacene-2,6-di-
carboxylate (5a): Yield 0.08 g (39%); m.p. 213–215 °C. 1H NMR
(300 MHz, [D6]DMSO): δ = 0.99–1.06 (m, 6 H, CH3CH2), 1.30 (t,
J = 7.2 Hz, 3 H, CH3CH2), 2.76 (s, 3 H, CH3), 4.00–4.08 (m, 2 H,
CH3CH2), 4.19–4.36 (m, 4 H, CH3CH2), 6.37 (s, 1 H, CH), 6.50
(d, J = 12.6 Hz, 1 H, CH), 6.76 (d, J = 14.1 Hz, 1 H, CH), 7.26–
7.50 (m, 13 H, ArH), 7.56 (d, J = 8.4 Hz, 1 H, ArH), 7.89 (d, J =
7.8 Hz, 1 H, ArH), 7.99 (t, J = 13.2 Hz, 1 H, CH) ppm. 13C NMR
(125 MHz, [D6]DMSO): δ = 12.84, 14.3, 59.7, 61.9, 99.3, 107.8,
112.6, 115.5, 116.7, 123.3, 124.5, 125.2, 128.1, 129.0, 129.5, 130.6,
131.1, 131.3, 133.8, 136.0, 137.6, 141.7, 144.2, 146.0, 149.7, 154.3,
165.5, 164.4, 165.8 ppm. LC-MS: m/z = 707 [M + H]+ .
C39H35BF2N3O4S (690.59): calcd. C 67.83, H 5.11, N 6.08; found
C 68.37, H 5.04, N 6.12.
Diethyl 4,4-Difluoro-3,5-bis[3-(1-methyl-1H-quinolin-2-ylidene)-
propen-1-yl]-1,7-diphenyl-4-bora-3a,4a-diaza-s-indacene-2,6-dicarb-
oxylate (6b): The residue was refluxed in EtOH, then the precipitate
was filtered and refluxed in EtOAc. The crude product was filtered
and recrystallized from CH3CN; yield 0.03 g (6%); m.p. 208–
1
210 °C. H NMR (300 MHz, [D6]CDCl3): δ = 0.99 (t, J = 4.2 Hz,
6 H, CH3CH2), 3.52 (s, 6 H, NCH3), 4.14 (q, J = 4.2 Hz, 4 H,
CH3CH2), 5.89 (d, J = 6.9 Hz, 2 H, CH), 6.55 (s, 1 H, CH), 6.83
(d, J = 6 Hz, 2 H, CH), 6.99–7.03 (m, 4 H), 7.09–7.14 (m, 4 H),
7.25–7.41 (m, 14 H), 8.11 (t, J = 7.8 Hz, 2 H, CH) ppm.
C53H46BF2N4O4: calcd. C 74.74, H 5.44, N 6.58; found C 74.63,
H 5.47, N 6.64.
Supporting Information (see footnote on the first page of this arti-
cle): Shape and energy of MOs of dyes 1, 4a and 4b; H NMR of
the obtained dyes.
Diethyl 4,4-Difluoro-5-methyl-3-[3-(1-methyl-1H-quinolin-2-ylidene)-
propen-1-yl]-1,7-diphenyl-4-bora-3a,4a-diaza-s-indacene-2,6-dicarb-
oxylate (6a): Yield 0.05 g (12 %); m.p. Ͼ 250 °C. 1H NMR
(300 MHz, [D6]DMSO): δ = 0.96–1.05 (m, 6 H, CH3CH2), 2.76 (s,
3 H, CH3), 3.87 (s, 3 H, CH3), 4.06 (q, 2 H, CH3CH2), 4.17 (m, 2
H, CH3CH2), 6.28 (s, 1 H, CH), 6.35 (d, J = 13.8 Hz, 1 H, CH),
6.80 (d, J = 13.8 Hz, 1 H, CH), 7.31–7.52 (m, 13 H, ArH), 7.68–
7.76 (m, 2 H, ArH), 7.82 (d, J = 8.7 Hz, 1 H, HetH), 7.91 (d, J =
9.3 Hz, 1 H, HetH), 8.45 (t, J = 14.1 Hz, 1 H, CH) ppm. 13C NMR
(125 MHz, [D6]DMSO): δ = 14.0, 14.3, 36.5, 59.6, 61.6, 97.6, 106.9,
108.2, 113.3, 116.6, 119.3, 124.7, 125.2, 128.1, 129.5, 130.6, 131.6,
132.7, 134.5, 135.5, 138.2, 140.6, 144.3, 146.2, 148.6, 151.7, 154.3,
164.6, 165.7 ppm. LC-MS: m/z = 685 [M + H]+. C41H37BF2N3O4
(684.57): calcd. C 71.94, H 5.45, N 6.14; found C 72.13, H 5.63, N
6.20.
1
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General Procedure for the Synthesis of Dyes 4b–6b: To a mixture
of BODIPY 1 (0.5 mmol) and the corresponding acylhemicyanine
(1.5 mmol; for 4b An = Br–, for 5b An = I–, for 6b An = TsO–) in
pyridine (4 mL), triethylamine (4 mL) was added and the reaction
mixture was heated at 100 °C for 15 min. After cooling to room
temperature, the mixture was evaporated to dryness and the residue
was treated as described below.
Diethyl 4,4-Difluoro-1,7-diphenyl-3,5-bis[3-(1,3,3-trimethylindolin-2-
ylidene)propen-1-yl]-4-bora-3a,4a-diaza-s-indacene-2,6-dicarboxyl-
ate (4b): The residue was refluxed in EtOH, filtered and washed
with hot ethanol. The crude product was dissolved in hot DMF
and precipitated by the addition of EtOH. Finally, the precipitate
was washed with EtOAc to give pure dye 4b; yield 0.1 g (22%);
1
m.p. Ͼ250 °C. H NMR (300 MHz, [D6]DMSO): δ = 0.94 (t, J =
4.5 Hz, 6 H, CH3CH2), 1.63 (s, 12 H, CH3), 3.37 (s, 6 H, NCH3),
4.12 (q, J = 4.1 Hz, 4 H, CH3CH2), 5.78 (d, J = 7.5 Hz, 2 H, CH),
6.45 (s, 1 H, CH), 6.87 (d, J = 9 Hz, 2 H, CH), 6.98 (t, J = 4.2 Hz,
2 H, HetH), 7.06 (d, J = 4.8 Hz, 2 H, HetH), 7.26 (t, J = 4.2 Hz,
2 H, HetH), 7.35–7.45 (m 12 H, ArH), 8.22 (t, J = 8.1 Hz, 2 H,
CH) ppm. 13C NMR (125 MHz, [D6]DMSO): δ = 14.0, 28.2, 29.9,
46.8, 61.1, 99.7, 108.4, 111.9, 115.9, 121.2, 121.7, 122.3, 128.4,
128.8, 128.9, 129.7, 132.6, 134.4, 139.0, 139.9, 142.3, 144.5, 150.7,
164.1, 166.1 ppm. C55H56BF2N4O4: calcd. C 74.57, H 6.37, N 6.32;
found C 74.72, H 6.48, N 6.41.
Diethyl 3,5-Bis[3-(3-ethyl-3H-benzothiazol-2-ylidene)propen-1-yl]-
4,4-difluoro-1,7-diphenyl-4-bora-3a,4a-diaza-s-indacene-2,6-dicarb-
oxylate (5b): The residue was refluxed in EtOH, then the precipitate
Eur. J. Org. Chem. 2012, 1825–1834
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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