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Synlett 2010(15): 2304-2310  
DOI: 10.1055/s-0030-1258050
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Elaborating Boron Dipyrromethene Dyes with Conjugated Polyaromatic Frameworks

Raymond Ziessel*, Thomas Bura, Jean-Hubert Olivier
Laboratoire de Chimie Organique et Spectroscopies Avancées (LCOSA, www-lmspc.u-strasbg.fr/lcosa), CNRS, UdS, ECPM, 25 Rue Becquerel, 67087 Strasbourg Cedex 2, France
e-Mail: ziessel@unistra.fr;
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Publikationsverlauf

Received 11 May 2010
Publikationsdatum:
30. August 2010 (online)

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Abstract

New difluoro-bora-diaza-s-indacenes were synthesized from tetramethyl derivatives following a sequence of reactions including Knoevenagel condensation, selective cross-coupling reactions in order to extend the delocalization pathway. The introduction of flexible chains bearing a terminal ester or based on polyethylene glycol insure a good solubility and import polarity which facilitates the purification procedures. Many polyaromatic subunits (pyrene, perylene, anthracene, naphtalene, ferrocene) were fused to the main central core of the Bodipy.

Key words

Bodipy - pyrene - perylene - anthracene - palladium - vinyl - ferrocene

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17

Compound 5b: ¹H (400.13 MHz, CDCl3): δ = 8.61 (d, ³ J = 8.2 Hz, 2 H), 8.53 (d, ³ J = 9.3 Hz, 2 H), 8.46 (d, ³ J = 16.6 Hz, 2 H), 8.27-8.16 (m, 6 H), 8.12 (d, ³ J = 9.3 Hz, 2 H), 8.09-7.96 (M, 6 H), 7.93 (d, ³ J = 8.2 Hz, 2 H), 7.89 (d, ³ J = 8.2 Hz, 2 H), 7.37 (d, ³ J = 8.2 Hz, 2 H), 7.00 (s, 2 H), 1.26 (s, 6 H). ¹³C{H} (100.61 MHz, CDCl3): δ = 158.2, 156.6, 156.2, 154.3, 155.5, 148.2, 136.8, 139.5, 132.8, 135.7, 133.6, 135.5, 134.9, 133.6, 130.7, 129.7, 124.9, 128.9, 127.5, 128.9, 127.0, 128.6, 127.0, 125.8, 124.7, 120.4, 96.9, 15.4. MS (EI): m/z (%) = 874.1 (100) [M]. Anal. Calcd for C53H34N2BF2I (Mr = 874.56): C, 72.79; H, 3.92; N, 3.20. Found: C, 72.44; H, 3.67; N, 3.02.

18

Compound 9b: ¹H (400 MHz, CDCl3): δ = 7.70 (d, ³ J = 16.3 Hz, 2 H), 7.56-7.48 (m, 10 H), 7.27 (d, ³ J = 8.2 Hz, ca. 2 H + solvent overlap), 7.18 (d, ³ J = 16.3 Hz, 2 H), 6.64 (s, 2 H), 4.16 (q, ³ J = 7.1 Hz, 2 H), 2.50 (t, ³ J = 7.0 Hz, 2 H), 2.39 (t, ³ J = 7.3 Hz, 2 H), 1.87-1.82 (m, 2 H), 1.72-1.68 (m, 2 H), 1.49 (s, 6 H), 1.28 (t, ³ J = 7.1 Hz, 3 H). ¹³C{¹H} (100 MHz, CDCl3): δ = 173.9, 152.9, 142.8, 139.2, 135.9, 135.4, 134.6, 133.8, 132.7, 132.4, 1296.3, 128.8, 125.3, 123.4, 120.2, 118.4, 91.8 (C≡C), 80.7 (C≡C), 60.8, 34.3, 28.5, 24.7, 19.6, 15.3 (CH3), 14.7 (CH3). MS (EI): m/z (%) = 811.0 (50) [M], 810.0 (100) [M], 808.0 (45) [M]. Anal. Calcd for C42H37N2BF2Br2O2 (Mr = 810.37): C, 62.25; H, 4.60; N, 3.46. Found: C, 61.89; H, 4.39; N, 3.27.

22

Compound 14: ¹H (400 MHz, CDCl3): δ = 8.72 (d, ³ J = 7.8 Hz, 1 H), 8.35 (d, ³ J = 7.6 Hz, 1 H), 8.38-8.03 (m, 14 H), 7.83-7.52 (m 12 H), 7.58-7.62 (m, 4 H), 7.35-7.26 (m, 4 H), 6.74 (s, 1 H), 6.72 (s, 1 H), 4.16 (q, ³ J = 7.2 Hz, 2 H), 2.52 (t, ³ J = 7.0 Hz, 2 H), 2.39 (t, ³ J = 7.2 Hz, 2 H), 1.92-1.80 (m, 2 H), 1.73-1.67 (m, 2 H), 1.48 (s, 6 H), 1.29 (t, ³ J = 7.1 Hz, 3 H). ¹³C{¹H} (100 MHz, CDCl3): δ = 173.8, 153.3, 152.5, 142.9, 142.4, 139.0, 136.9, 132.7, 132.5, 132.4, 131.6, 130.1, 128.9, 128.0, 127.8, 127.7, 126.7, 126.1, 125.0, 121.4, 121.2, 121.0, 118.6, 96.5 (C≡C), 91.9 (C≡C), 91.4 (C≡C) 90.6 (C≡C), 90.2 (C≡C), 80.8 (C≡C), 60.8, 34.3, 28.5, 27.3, 24.7, 19.6, 15.30 (CH3), 14.7 (CH3). MS (EI): m/z (%) = 1151.2 (90) [M], 1150.2 (100) [M]. Anal. Calcd for C82H57N2BF2O2 (Mr = 1151.15): C, 85.56; H, 4.99; N, 2.43. Found: C, 85.33; H, 4.62; N, 2.15.