Optical Properties of Pyrrolopyrrole Cyanines
3
C2D2Cl4): δ = 14.45 (s, 2 H, NH), 7.84 (d, J = 8.9 Hz, 2 H, 4-H),
6.6 Hz, 4 H, OCH2), 1.89 (m, 4 H, OCH2CH2), 1.56 [m, 4 H,
7.76 (d, J = 1.7 Hz, 2 H, 5-H), 7.67 (m, 4 H, AAЈ), 7.61 (dd, 3J = O(CH2)2CH2], 1.5–1.3 (m, 16 H, alkyl), 0.96 (m, 6 H, CH3) ppm.
4
4
3
8.8, J = 1.7 Hz, 2 H, 7-H), 7.57 (d, J = 8.9 Hz, 2 H, 3-H), 7.53
UV/Vis/NIR (CHCl3): λmax (ε)
=
761 (229000), 689
(d, 3J = 8.8 Hz, 2 H, 8-H), 7.41 (m, 4 H, PhH), 7.24 (m, 6 H, PhH),
(48000 m–1 cm–1) nm. MALDI-MS: calcd. for C56H52B2Br2F4N6O2
7.13 (m, 4 H, XXЈ), 4.07 (t, J = 6.4 Hz, 4 H, OCH2), 1.82 (m, 4 [M + H]+ 1097.3; found 1097.9. C56H52B2Br2F4N6O2 (1098.49):
H, OCH2CH2), 1.47 [m, 4 H, O(CH2)2CH2], 1.4–1.2 (m, 16 H, calcd. C 61.23, H 4.77, N 7.65; found C 61.19, H 4.81, N 7.70.
alkyl), 0.85 (m, 6 H, CH3) ppm. UV/Vis/NIR (CHCl3): λmax (ε) =
3
Compound 4c: Column chromatography (CH2Cl2) afforded 4c as a
752 (166000), 681 (59000 m–1 cm–1) nm. C72H64N6O2 (1045.34):
green crystalline powder in 34% yield (relative to the crude product
calcd. C 82.73, H 6.17, N 8.04; found C 82.41, H 6.08, N 8.01.
1
3
3c). H NMR (400 MHz, C2D2Cl4): δ = 8.44 (d, J = 9.5 Hz, 2 H,
8-H), 7.68 (m, 6 H, 5-H, AAЈ), 7.56 (m, 2 H, 7-H), 7.55 (s, 2 H, 3-
H), 7.50 (m, 6 H, Ph), 7.38 (m, 4 H, Ph), 6.99 (m, 4 H, XXЈ), 3.99
Compound 3f: Column chromatography (CH2Cl2 to CH2Cl2/ethyl
acetate, 50:1) afforded 3f as a green crystalline powder in 19%
yield. 1H NMR (600 MHz, C2D2Cl4, 100 °C): δ = 7.70 (m, 4 H,
3
(t, J = 6.6 Hz, 4 H, OCH2), 1.75 (m, 4 H, OCH2CH2), 1.42 [m, 4
AAЈ), 7.68 (d, J = 8.8 Hz, 2 H, 4-H), 7.29 (d, 4J = 2.1 Hz, 2 H,
3
H, O(CH2)2CH2], 1.35–1.1 (m, 16 H, alkyl), 0.82 (m, 6 H, CH3)
3
4
7-H), 7.12 (m, 4 H, XXЈ), 7.03 (dd, J = 8.8, J = 2.1 Hz, 2 H, 5-
H), 4.10 (t, 3J = 6.4 Hz, 4 H, OCH2), 3.85 (s, 6 H, OCH3), 1.84
(m, 4 H, OCH2CH2), 1.51 [m, 4 H, O(CH2)2CH2], 1.45–1.25 (m,
16 H, alkyl), 0.91 (m, 6 H, CH3) ppm. UV/Vis/NIR (CHCl3): λmax
(ε) = 746 (106000), 676 (48000 m–1 cm–1) nm. MALDI-MS: calcd.
for C54H57N6O4S2 [M + H]+ 917.4; found 916.3. C54H56N6O4S2
(917.19): calcd. C 70.71, H 6.15, N 9.16, S 6.99; found C 70.57, H
6.18, N 9.00, S 7.09.
ppm. UV/Vis/NIR (CHCl3): λmax (ε)
= 767 (237000), 693
(51000 m–1 cm–1) nm. MALDI-MS: calcd. for C68H60B2Cl2F4N6O2
[M + H]+ 1161.4; found 1161.6. C68H60B2Cl2F4N6O2 (1161.78):
calcd. C 70.30, H 5.21, N 7.23; found C 70.36, H 5.37, N 7.28.
Compound 4d: The crude product was digested in methanol, col-
lected by filtration, and washed with methanol. Drying in air gave
4d in 86% yield as a green crystalline powder. 1H NMR (600 MHz,
3
3
C2D2Cl4, 100 °C): δ = 8.47 (d, J = 8.9 Hz, 2 H, 8-H), 8.01 (d, J
4
3
Compound 3g: Column chromatography (CH2Cl2 Ǟ CH2Cl2/ethyl
acetate, 100:1) afforded 3g as a green crystalline powder in 16%
yield. 1H NMR (400 MHz, C2D2Cl4): δ = 12.93 (s, 2 H, NH), 7.64
(m, 6 H, 4-H, AAЈ), 7.55 (d, J = 1.7 Hz, 2 H, 7-H), 7.28 (dd, J
= 8.5, 4J = 1.7 Hz, 2 H, 5-H), 7.08 (m, 4 H, XXЈ), 4.02 (t, 3J =
6.4 Hz, 4 H, OCH2), 2.48 (s, 6 H, SCH3), 1.78 (m, 4 H, OCH2CH2),
1.43 [m, 4 H, O(CH2)2CH2], 1.37–1.15 (m, 16 H, alkyl), 0.84 (m, 6
H, CH3) ppm. UV/Vis/NIR (CHCl3): λmax (ε) = 751 (116000), 681
(52000 m–1 cm–1) nm. C54H56N6O2S4 (949.32): calcd. C 68.32, H
5.95, N 8.85, S 13.51; found C 67.95, H 5.81, N 9.00, S 13.57.
= 9.1 Hz, 2 H, 4-H), 7.83 (d, J = 1.7 Hz, 2 H, 5-H), 7.74 (dd, J
= 8.9, 4J = 1.7 Hz, 2 H, 7-H), 7.71 (d, J = 9.1 Hz, 2 H, 3-H), 7.68
3
(m, 4 H, AAЈ), 7.53 (m, 4 H, Ph), 7.33 (m, 6 H, Ph), 7.05 (m, 4 H,
XXЈ), 4.11 (t, 3J = 6.6 Hz, 4 H, OCH2), 1.86 (m, 4 H, OCH2CH2),
1.52 [m, 4 H, O(CH2)2CH2], 1.45–1.25 (m, 16 H, alkyl), 0.92 (m, 6
H, CH3) ppm. UV/Vis/NIR (CHCl3): λmax (ε) = 778 (284000), 703
(59000 m–1 cm–1) nm. C72H62B2F4N6O2 (1140.93): calcd. C 75.80,
H 5.48, N 7.37; found C 75.54, H 5.55, N 7.51.
4
3
Compound 4f: Column chromatography (CH2Cl2) afforded 4f as a
green crystalline powder in 63% yield. 1H NMR (400 MHz,
Compound 3h: Column chromatography (CH2Cl2) afforded 3h as a
3
C2D2Cl4): δ = 7.87 (d, J = 9.2 Hz, 2 H, 4-H), 7.64 (m, 4 H, AAЈ),
green crystalline powder in 65% yield. 1H NMR (400 MHz,
4
3
4
7.16 (d, J = 2.4 Hz, 2 H, 7-H), 7.05 (dd, J = 9.2, J = 2.4 Hz, 2
H, 5-H), 7.03 (m, 4 H, XXЈ), 4.08 (t, 3J = 6.6 Hz, 4 H, OCH2),
3.83 (s, 6 H, OCH3), 1.84 (m, 4 H, OCH2CH2), 1.51 [m, 4 H,
O(CH2)2CH2], 1.45–1.25 (m, 16 H, alkyl), 0.91 (m, 6 H, CH3) ppm.
3
C2D2Cl4): δ = 12.91 (s, 2 H, NH), 7.89 (m, 2 H, 7-H), 7.80 (d, J
= 8.6 Hz, 2 H, 4-H), 7.92 (m, 6 H, 5-H, AAЈ), 7.06 (m, 4 H, XXЈ),
4.02 (t, J = 6.6 Hz, 4 H, OCH2), 1.79 (m, 4 H, OCH2CH2), 1.44
[m, 4 H, O(CH2)2CH2], 1.40–1.15 (m, 16 H, alkyl), 0.85 (m, 6 H,
CH3) ppm. UV/Vis/NIR (CHCl3): λmax (ε) = 726 (130000), 659
(47000 m–1 cm–1) nm. C54H50B2F6N6O2S2 (1014.76): calcd. C 65.31,
H 5.07, N 8.46; found C 66.43, H 5.54, N 8.86.
3
UV/Vis/NIR (CHCl3): λmax (ε)
=
745 (171000), 674
(54000 m–1 cm–1) nm. MALDI-MS: calcd. for C54H54B2F4N6O4S2
1013.4 [M + H]+, 1035.4 [M + Na]+; found 1013.2, 1035.2.
C54H54B2F4N6O4S2 (1012.79): calcd. C 64.04, H 5.37, N 8.30;
found C 63.98, H 5.35, N 8.21.
Compound 3j: The solubility of 3j in common solvents was too low
to allow purification by chromatography. The crude product was
digested in acetone, collected by filtration, and washed with acet-
one. Drying in air yielded 3j, which was pure enough to perform
further reactions. MALDI-MS: calcd. for C60H56N6O4 + 1 [M +
H]+ 925.4; found 924.9.
Compound 4g: Column chromatography (CH2Cl2) afforded 4g as a
dark-green crystalline powder in 14% yield (relative to the crude
product 3g). 1H NMR (400 MHz, C2D2Cl4): δ = 7.78 (d, 3J =
4
8.8 Hz, 2 H, 4-H), 7.62 (m, 4 H, AAЈ), 7.49 (d, J = 1.7 Hz, 2 H,
7-H), 7.28 (dd, 3J = 8.8, 4J = 1.7 Hz, 2 H, 5-H), 7.00 (m, 4 H,
3
XXЈ), 4.00 (t, J = 6.6 Hz, 4 H, OCH2), 2.46 (s, 6 H, SCH3), 1.78
General Procedure for the Synthesis of BF2–PPCy Dyes 4: H-PPCy
dye 3 (1 mmol) and N,N-di-isopropylethylamine (20 mmol) were
heated to reflux in CH2Cl2 (100 mL). BF3·Et2O (40 mmol) was
added, and the mixture was heated to reflux for 10 min. The mix-
ture was washed with water and dried with MgSO4. After removal
of the solvent, the crude product was purified by column
chromatography. Synthesis and physical data of 4a, 4e, and 4i have
been previously reported.[4]
(m, 4 H, OCH2CH2), 1.43 [m, 4 H, O(CH2)2CH2], 1.37–1.15 (m,
16 H, alkyl), 0.84 (m, 6 H, CH3) ppm. UV/Vis/NIR (CHCl3): λmax
(ε) = 753 (165000), 683 (54000 m–1 cm–1) nm. MALDI-MS: calcd.
for C54H54B2F4N6O2S4 1045.3 [M
+
H]+; found 1044.8.
C54H54B2F4N6O2S4 (1044.91): calcd. C 62.07, H 5.21, N 8.04;
found C 61.70, H 5.36, N 8.16.
Compound 4h: Column chromatography (CH2Cl2) afforded 4h as a
green crystalline powder in 79% yield. 1H NMR (600 MHz,
C2D2Cl4, 118 °C): δ = 8.17 (m, 2 H, 4-H), 7.98 (m, 2 H, 7-H), 7.70
Compound 4b: The crude product was digested in methanol, col-
lected by filtration, and washed with methanol. Drying in air gave
4b in 74% yield (relative to the crude product 3b). 1H NMR
3
(m, 2 H, 5-H), 7.67 (m, 4 H, AAЈ), 7.05 (m, 4 H, XXЈ), 4.10 (t, J
3
(400 MHz, C2D2Cl4, 100 °C): δ = 8.42 (d, J = 9.5 Hz, 2 H, 8-H),
= 6.6 Hz, 4 H, OCH2), 1.84 (m, 4 H, OCH2CH2), 1.51 [m, 4 H,
O(CH2)2CH2], 1.45–1.15 (m, 16 H, alkyl), 0.91 (m, 6 H, CH3) ppm.
8.01 (d, J = 9.0 Hz, 2 H, 4-H), 7.89 (d, 4J = 2.2 Hz, 2 H, 5-H),
3
3
4
3
7.77 (dd, J = 9.5, J = 2.2 Hz, 2 H, 7-H), 7.75 (d, J = 9.0 Hz, 2 UV/Vis/NIR (CHCl3): λmax (ε)
=
719 (175000), 654
H, 3-H), 7.72 (m, 4 H, AAЈ), 7.08 (m, 4 H, XXЈ), 4.14 (t, 3J = (40000 m–1 cm–1) nm. C54H48B2F10N6O2S2 (1088.73): calcd.
C
Eur. J. Org. Chem. 2011, 3421–3429
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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