Synthesis and Optoelectrochemical Properties of Stilbenophanes Having Carbazole Moieties

Abstract

A series of stilbenophanes having N-arylated carbazole moieties possessing small and large cavities have been synthesized via McMurry coupling of the corresponding dialdehyde derived from N-arylation of carbazole with various dibromide followed by formylation. The electrochemical, photophysical, and complexation properties of all the stilbenophanes with electron-deficient guest molecules like TCNQ, TCNE, and PQT were also carried out at different concentrations.

Key words

carbazole - stilbenophanes - fluorescence - redox potential

• References and Notes

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• 21 Compound 11a White solid; yield 82%; mp 110–112 °C. ¹H NMR (300 MHz, CDCl₃): δ = 1.63 (s, 3 H), 7.30 (t, 4 H, J = 7.5 Hz), 7.44 (t, 4 H, J = 7.8 Hz), 7.51–7.56 (m, 6 H), 7.62 (s, 1 H), 8.15 (d, 4 H, J = 7.8 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 21.6, 109.8, 120.2, 120.5, 122.5, 123.6, 126.1, 126.6, 139.2, 140.7, 141.7. MS (EI): m/z = 422 [M⁺]. Anal. Calcd (%) for C₃₁H₂₂N₂: C, 88.12; H, 5.25; N, 6.63. Found: C, 88.24; H, 5.34; N, 6.78.
• 22 Dialdehyde 16a White solid; yield 72%; mp 102–104 °C. ¹H NMR (300 MHz, CDCl₃): δ = 1.65 (s, 3 H), 7.26 (s, 1 H), 7.38–7.43 (m, 2 H), 7.52–7.59 (m, 8 H), 7.99 (dd, 2 H, J = 8.6, 1.2 Hz), 8.22 (d, 2 H, J = 7.5 Hz), 8.68 (s, 2 H), 10.13 (s, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.6, 110.0, 110.3, 120.9, 121.6, 122.7, 123.4, 123.9, 127.3, 127.5, 127.7, 129.8, 138.4, 141.6, 142.6, 144.2, 191.6. MS (EI): m/z = 478 [M⁺]. Anal. Calcd (%) for C₃₃H₂₂N₂O₂: C, 82.83; H, 4.63; N, 5.85. Found: C, 82.96; H, 4.72; N, 5.94.
• 23 Stilbenophane 1a White solid; yield 18%; mp 172–173 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.48 (s, 6 H), 6.83 (s, 4 H), 7.18 (d, 4 H, J = 8.4 Hz), 7.27–7.43 (m, 16 H), 7.49 (d, 4 H, J = 8.1 Hz), 7.57 (s, 2 H), 8.01 (s, 4 H), 8.08 (d, 4 H, J = 7.5 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 21.5, 109.4, 109.8, 120.2, 120.4, 121.4, 122.1, 123.4, 123.6, 126.0, 126.3, 126.7, 129.4, 130.0, 138.8, 139.5, 140.5, 141.6. MS–FAB: m/z = 894 [M⁺]. Anal. Calcd (%) for C₆₆H₄₄N₄: C, 88.76; H, 4.97; N, 6.27. Found: 88.92; H, 4.82; N, 6.42.
• 24 Stilbenophane 1b White solid; yield 15%; mp 164–166 °C. ¹H NMR (300 MHz, CDCl₃): δ = 2.43 (s, 6 H), 3.63 (s, 6 H), 6.84 (s, 4 H), 7.14 (d, 4 H, J = 8.3 Hz), 7.22–7.39 (m, 16 H), 7.47 (d, 4 H, J = 8.1 Hz), 8.02 (s, 4 H), 8.06 (d, 4 H, J = 7.6 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 21.2, 52.8, 109.6, 109.9, 120.1, 120.6, 121.7, 122.4, 123.7, 123.9, 126.0, 126.4, 126.9, 129.7, 130.3, 138.7, 139.4, 140.5, 151.2. MS–FAB: m/z = 954 [M⁺]. Anal. Calcd (%) for C₆₈H₄₈N₄O₂: C, 85.69; H, 5.08; N, 5.88. Found: C, 85.82; H, 5.22; N, 5.98.
• 25 Stilbenophane 2 White solid; yield 17%; mp 186–187 °C. ¹H NMR (300 MHz, CDCl₃): δ = 6.81 (s, 4 H), 7.18 (d, 4 H, J = 8.3 Hz), 7.24–7.40 (m, 12 H), 7.47 (d, 4 H, J = 8.1 Hz), 7.63 (d, 4 H, J = 6.7 Hz), 7.87 (t, 2 H, J = 6.8 Hz), 8.04 (s, 4 H), 8.10 (d, 4 H, J = 7.6 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 109.8, 110.4, 116.7, 120.2, 120.5, 121.6, 122.2, 123.6, 126.2, 126.6, 129.8, 130.4, 138.8, 139.6, 140.6, 151.6. MS–FAB: m/z = 868 [M⁺]. Anal. Calcd (%) for C₆₂H₃₈N₆: C, 85.89; H, 4.42; N, 9.69. Found: C, 85.72; H, 4.30; N, 9.60.
• 26 Stilbenophane 3 White solid; yield 15%; mp 191–193 °C. ¹H NMR (300 MHz, CDCl₃): δ = 6.85 (s, 4 H), 7.23–7.47 (m, 20 H), 7.64 (d, 4 H, J = 6.9 Hz), 7.99 (s, 4 H), 8.08 (d, 4 H, J = 6.6 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 109.8, 110.4, 120.3, 121.1, 121.4, 122.6, 123.8, 123.8, 126.4, 126.8, 129.5, 130.7, 136.0, 140.6, 141.7. MS–FAB: m/z = 878 [M⁺]. Anal. Calcd (%) for C₆₀H₃₆N₄S₂: C, 82.16; H, 4.14; N, 6.39. Found: C, 82.27; H, 4.31; N, 6.52.
• 27 Stilbenophane 4 White solid; yield 12%; mp 191–193 °C. ¹H NMR (300 MHz, CDCl₃): δ = 1.45 (t, 6 H, J = 7.1 Hz), 4.40 (q, 4 H, J = 7.1 Hz), 6.87 (s, 4 H), 7.08 (s, 4 H), 7.12–7.27 (m, 8 H), 7.31–7.52 (m, 12 H), 7.61 (d, 4 H, J = 6.9 Hz), 7.72 (s, 4 H), 7.93 (d, 4 H, J = 8.1 Hz), 8.08 (d, 4 H, J = 6.6 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 13.7, 38.1, 109.1, 110.2, 111.2, 120.1, 121.2, 121.4, 122.3, 122.6, 123.4, 123.7, 126.4, 124.6, 126.7, 126.9, 129.4, 130.6, 136.2, 140.4, 141.8. MS–FAB: m/z = 1100 [M⁺]. Anal. Calcd (%) for C₈₀H₅₄N₆: C, 87.40; H, 4.95; N, 7.64. Found: C, 87.54; H, 4.82; N, 7.51.
• 28 Stilbenophane 5 White solid; yield 15%; mp 202–204 °C. ¹H NMR (300 MHz, CDCl₃): δ = 0.39 (t, 12 H, J = 7.2 Hz), 2.00 (q, 8 H, J = 7.2 Hz), 6.84 (s, 4 H), 7.26–7.35 (m, 8 H), 7.46 (t, 4 H, J = 6.9 Hz), 7.56 (s, 4 H), 7.60–7.68 (m, 12 H), 7.93 (d, 4 H, J = 8.1 Hz), 8.11 (s, 4 H), 8.18 (d, 4 H, J = 7.8 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 8.6, 30.9, 56.5, 109.1, 110.2, 120.3, 121.8, 122.9, 125.2, 126.1, 129.8, 130.4, 133.8, 136.8, 138.2, 139.7, 140.8, 142.6, 146.5, 148.8, 151.7, 153.5. MS–FAB: 1154 [M⁺]. Anal. Calcd (%) for C₈₆H₆₄N₄: C, 89.55; H, 5.59; N, 4.86. Found: C, 89.72; H, 5.74; N, 4.96.
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• 36 Determination of the Association Constant by UV-Vis Spectroscopy (Benesi–Hildebrand Method) In a typical experiment, 3 mL of a standard stock solution of the cyclophane in MeCN–CH₂Cl₂ was placed in a quartz cuvette. A known amount of the electron-deficient guest molecule was added in incremental amounts and the changes in absorbance of the CT bands were recorded. Table 4 shows the charge-transfer complexation studies of stilbenophanes 2 with various concentrations of TCNQ. Plots of [concn of cyclophane]/absorbance vs. 1/concentration of guest were linear (Figure 7). From the slope and the intercept values K _a (K _a = intercept × slope^–1) and ε (ε = intercept^–1) were evaluated (Table 4). The plots were linear, suggesting that the predominant species in solution was a 1:1 complex.
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