Panchromatic Push–Pull Dyes of Elongated Form from Triphenylamine, Diketopyrrolopyrrole, and Tetracyanobutadiene Modules

Abstract

Several symmetrical and unsymmetrical thiophene-functionalized diketopyrrolopyrrole chromophores bearing a bis(p-methoxyphenyl)-p-phenylamine substituent were synthesized through palladium-catalyzed cross-coupling reactions. Mono-substitution and di-substitution occur using either alkyne or borolane groups, allowing the preparation of mixed systems. The alkyne derivatives could be prepared in high yields, and are versatile building blocks for the [2+2] cy­cloaddition of tetracyanoethylene, leading to 1,1,4,4-tetracyanobuta-1,3-diene derivatives. These interesting push–pull molecules exhibit a rich redox activity, which is understandable in light of the behavior of appropriate reference compounds. These innovative and rationally designed scaffolds are highly colored, exhibiting high absorption coefficients and spanning an absorption range of more than 600 nm of the UV/Vis electromagnetic spectrum.

Key words

cross-coupling reactions - cycloaddition reactions - push–pull molecules - panchromatic dyes - redox properties

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• 25 Compound 6: Tetracyanoethylene (41.0 mg, 0.320 mmol, 1.9 equiv) was added to a solution of 5 (144.3 mg, 0.169 mmol) in 1,2-dichloroethane (25 mL). The reaction medium was stirred at 40 °C for 87 h, then evaporated to dryness. Purification by column chromatography (SiO₂, CH₂Cl₂–petroleum ether, 80:20 to 100:0 with 2% Et₃N), followed by recrystallization (THF–n-pentane) afforded 6 (129.6 mg, 78%) as a black powder. ¹H NMR (300 MHz, CDCl₃): δ = 0.83–0.91 (m, 12 H), 1.21–1.40 (m, 16 H), 1.78–1.92 (m, 2 H), 3.84 (s, 6 H), 4.00–4.06 (m, 4 H), 6.81 (d, ³ J = 9.2 Hz, 2 H), 6.92 (d, ³ J = 8.9 Hz, 4 H), 7.16 (d, ³ J = 8.9 Hz, 4 H), 7.33 (dd, ³ J = 5.0, 4.8 Hz, 1 H), 7.67 (d, ³ J = 9.2 Hz, 2 H), 7.77 (dd, ³ J = 5.0 Hz, ⁴ J = 1.0 Hz, 1 H), 7.84 (d, ³ J = 4.5 Hz, 1 H), 9.06 (d, ³ J = 4.5 Hz, 1 H), 9.17 (dd, ³ J = 4.1 Hz, ⁴ J = 0.8 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 10.5, 14.1, 23.2, 23.5, 23.6, 28.3, 28.4, 30.1, 30.2, 39.1, 39.8, 46.2, 46.4, 55.7, 80.1, 108.6, 112.0, 113.0, 113.0, 113.1, 113.9, 115.5, 116.8, 120.0, 125.4, 128.3, 129.1, 129.4, 132.1, 133.3, 135.6, 136.0, 137.1, 137.7, 138.1, 140.2, 144.4, 154.8, 157.5, 158.5, 161.0, 161.9, 162.1. UV/Vis (toluene): λ (ε, M^–1cm^–1) = 691 (37 200), 636 (27 300), 483 (31 500), 333 (16 000) nm. MS (EI): m/z (%) calcd for C₅₈H₅₇N₇O₄S₂: 979.39 (100); found 979.2 (100), 953.2 (25). Anal. Calcd for C₅₈H₅₇N₇O₄S₂ (980.25): C, 71.07; H, 5.86, N, 10.00. Found: C, 70.84; H, 5.47; N, 9.77.
• 26 Compound 8: Tetracyanoethylene (23.3 mg, 0.182 mmol, 3.4 equiv) was added to a solution of 7 (64.2 mg, 0.054 mmol) in 1,2-dichloroethane (15 mL). The reaction medium was stirred at 40 °C for 18 h, then evaporated to dryness. Purification by column chromatography (Al₂O₃; CH₂Cl₂–petroleum ether, 70:30 to 80:20), followed by recrystallization (THF–n-pentane) afforded 8 (41.6 mg, 54%) as a brownish black powder. ¹H NMR (300 MHz, CDCl₃): δ = 0.83–0.91 (m, 12 H), 1.21–1.36 (m, 16 H), 1.78–1.84 (m, 2 H), 3.82 (s, 12 H), 4.02 (d, ³ J = 7.9 Hz, 4 H), 6.81 (d, ³ J = 9.2 Hz, 4 H), 6.91–6.95 (m, 8 H), 7.13–7.18 (m, 8 H), 7.66 (d, ³ J = 9.4 Hz, 4 H), 7.85 (d, ³ J = 4.6 Hz, 2 H), 9.20 (d, ³ J = 4.6 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 10.4, 14.1, 23.2, 23.4, 28.2, 30.0, 39.7, 46.6, 55.7, 76.5, 81.8, 111.6, 112.7, 112.9, 113.1, 113.8, 115.5, 116.9, 119.8, 128.3, 132.1, 137.1, 137.3, 137.7, 138.8, 139.0, 140.0, 154.9, 157.7, 158.6, 161.1, 161.6. UV/Vis (toluene): λ (ε, M^–1cm^–1) = 749 (48 100), 689 (36 500), 472 (52 700), 393 (27 400) nm. MS (EI): m/z (%) calcd for C₈₆H₇₄N₁₂O₆S₂: 1434.53 (100), 1435.53 (99.3); found: 1435.4 (100), 1408.4 (35), 1382.4 (15). Anal. Calcd for C₈₆H₇₄N₁₂O₆S₂ (1434.71): C, 71.94; H, 5.20, N, 11.71. Found: C, 71.72; H, 4.84; N, 11.49.
• 27 Compound 14: Tetracyanoethylene (31.0 mg, 0.242 mmol, 2.3 equiv) was added to a solution of 13 (100.4 mg, 0.105 mmol) in 1,2-dichloroethane (25 mL). The round-bottom flask was equipped with a condenser and the mixture was stirred at 50 °C for 48 h. The reaction medium was extracted with CH₂Cl₂, washed with H₂O, and dried with brine and over Na₂SO₄. Purification by column chromatography (SiO₂; petroleum ether–EtOAc, 85:15 to 75:25), followed by precipitation from CH₂Cl₂–MeOH afforded 14 (100.0 mg, 88%) as a black powder. ¹H NMR (400 MHz, CDCl₃): δ = 0.84–0.93 (m, 12 H), 1.21–1.40 (m, 16 H), 1.81–1.87 (m, 1 H), 1.92–1.99 (m, 1 H), 3.82 (s, 6 H), 3.92 (s, 3 H), 4.02–4.08 (m, 4 H), 6.88 (d, ³ J = 8.9 Hz, Dn_{AB syst} = 94.0 Hz, 4 H), 6.91 (d, ³ J = 8.8. Hz, 2 H), 7.05 (d, ³ J = 9.1 Hz, 2 H), 7.11 (d, ³ J = 8.9 Hz, Dn_{AB syst} = 94.0 Hz, 4 H), 7.41 (d, ³ J = 4.4 Hz, 1 H), 7.49 (d, ³ J = 8.8 Hz, 2 H), 7.82 (d, ³ J = 9.1 Hz, 2 H), 7.83 (d, ³ J = 4.7 Hz, 1 H), 9.08 (d, ³ J = 4.6 Hz, 1 H), 9.35 (d, ³ J = 4.3 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 10.52, 10.61, 14.15, 14.21, 23.2, 23.5, 23, 7, 28.3, 28, 5, 30.1, 30.4, 39.3, 39.8, 46.3, 46.5, 55.7, 56.1, 77.9, 78.8, 83.4, 108.5, 111.8, 112.2, 112.5, 113.1, 114.1, 115.0, 115.1, 115.9, 119.3, 123.4, 123.7, 123.9, 126.4, 127.4, 127.5, 127.6, 132.3, 133.8, 135.1, 135.9, 137.8, 139.8, 141.3, 145.0, 150.5, 154.9, 156.0, 156.9, 160.9, 162.3, 165.0, 165.4. UV/Vis (toluene): λ (ε, M^–1cm^–1) = 796 (61 200), 549 (6 300), 372 (39 200) nm. UV/Vis (THF): λ (ε, M^–1cm^–1) = 763 (52 600), 541 (3 400), 370 (38 900) nm. MS (EI): m/z (%) calcd for C₆₅H₆₃N₇O₅S₂: 1085.2 (100), 1086.44 (71); found: 1085.2 (100), 1086.2 (75). Anal. Calcd for C₆₅H₆₃N₇O₅S₂ (1085.43): C, 71.86; H, 5.85, N, 9.03. Found: C, 71.60; H, 5.69; N, 8.77.
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