Elaborating Boron Dipyrromethene Dyes with Conjugated Polyaromatic Frameworks

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

References and Notes

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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.