Dissymmetric Bay-Functionalized Perylenediimides

Abstract

We report the synthesis of perylenediimide (PDI)-based ­donor–acceptor hybrids through dissymmetric bay functionalization of PDIs. The dissymmetric bay-functionalized di- and trisubstituted PDIs were characterized by using one- and two-dimensional NMR spectroscopy. Density functional theory calculations revealed (i) an energy gap between the HOMO and LUMO in the range 2.14–2.34 eV, beneficial for charge-transfer properties; and (ii) a twist angle between the two naphthalene units in the range 17–26°, which might be beneficial for disruption of co-facial stacking of the PDI.

Key words

perylenediimide - dissymmetric functionalization - bay functionalization - nitration - density functional theory

• References and Notes

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• 24 Dissymmetric Trisubstituted PDI 2; Typical ProcedurePDI 9 (300 mg, 0.51 mmol) was dissolved in CH₂Cl₂ (30 mL). HNO₃ (771.56 μL, 8.60 mmol), CAN (280 mg, 0.51 mmol), and H₂SO₄ (984.95 μL, 9.65 mmol) were added, and the mixture was stirred at r.t. for 10 h. When the reaction was complete (TLC), H₂O was added to the mixture and the organic layer was repeatedly extracted with water (pH 7.0), dried (Na₂SO₄), and concentrated. The crude product was purified by column chromatography (silica gel, 70% CHCl₃–hexane).
• 25 PDI 2Dark-blue solid; yield: 316 mg (0.468 mmol, 91.3%); R_f = 0.40 (CHCl₃–hexane, 7:3). IR (ATR): 3287, 2966, 2933, 2875, 2360, 2126, 1701, 1661, 1595, 1543, 1459, 1411, 1357, 1313, 1250, 1200, 1070, 999, 928, 809 cm^–1. ¹H NMR (500 MHz, CDCl₃, 25 °C): δ = 9.12 (s, 1 H, perylene ArH), 8.85 (s, 1 H, perylene ArH), 8.55 (d, J = 8.0 Hz, 1 H, perylene ArH), 8.53 (s, 1 H, perylene ArH), 8.30 (d, J = 8.0 Hz, 1 H, perylene ArH), 5.07 (d, J = 2.0 Hz, 2 H, OCH₂), 5.01–5.06 (m, 2 H, ethylpropyl), 2.69 (t, J = 2.5 Hz, 1 H, –C≡H), 2.21–2.27 (m, 4 H, ethylpropyl), 1.92–1.98 (m, 4 H, ethylpropyl), 0.91 (t, J = 7.5 Hz, 6 H, ethylpropyl), 0.94 (t, J = 7.5 Hz, 6 H, ethylpropyl). ¹³C NMR (125 MHz, CDCl₃, 25 °C): δ = 11.23, 11.35, 24.84, 25.03, 56.92, 58.35, 58.60, 75.76, 78.60, 116.31, 123.77, 126.68, 127.10, 127.44, 128.11, 129.56, 129.75, 148.07, 148.61, 157.79. Emission = 536 nm; Absorption = 561 nm (MeCN–H₂O with f _w = 50 vol%).
• 26 Dissymmetric Disubstituted PDI 1; General ProcedurePDI 9 (50 mg, 0.085 mmol) was dissolved in CH₂Cl₂ (5 mL). HNO₃ (42.86 μL, 0.48 mmol), CAN (22.22 mg, 0.04 mmol), and H₂SO₄ (22.80 μL, 0.21 mmol) were added, and the mixture was stirred at r.t. for 4 h. When the reaction was complete (TLC), H₂O was added to the mixture and the organic layer was repeatedly extracted with H₂O (pH 7.0), dried (Na₂SO₄), and concentrated. The crude product was purified by column chromatography (silica gel, 70% CHCl₃–hexane).
• 27 PDI 1Dark-purple solid; yield: 48.2 mg (0.076 mmol, 89.6%); R_f = 0.26 (CHCl₃–hexane, 7:3); IR (ATR): 3265, 2924, 2853, 2361, 1699, 1659, 1594, 1461, 1412, 1315, 1251, 1070, 808, 743 cm^–1. ¹H NMR (500 MHz, CDCl₃, 25 °C): δ = 9.05 (s, 1 H, perylene ArH), 8.78 (d, J = 8.0 Hz, 1 H, perylene ArH), 8.68 (d, J = 8.0 Hz, 1 H, perylene ArH), 8.64 (d, J = 8.0 Hz, 2 H, perylene ArH), 8.51 (s, 1 H, perylene ArH), 5.06–5.10 (m, 2 H, ethylpropyl), 5.05 (d, J = 2 Hz, 2 H, OCH₂), 2.66 (t, J = 2.5 Hz, 1 H, –C≡H), 2.21–2.30 (m, 4 H, ethylpropyl), 1.90–1.99 (m, 4 H, ethylpropyl), 0.90–0.95 (m, 12 H, ethylpropyl). ¹³C NMR (125 MHz, CDCl₃, 25 ºC): δ = 11.28, 11.35, 24.93, 25.04, 56.64, 58.05, 58.09, 76.14, 78.17, 117.84, 123.43, 124.30, 124.76, 126.88, 128.08, 128.45, 129.67, 132.15, 135.41, 148.04, 156.62. Emission = 542 nm; Absorption = 560 nm (MeCN–H₂O with f _w = 50 vol%).
• 28 PDI 3Dark-purple solid; yield: 50.7 mg (0.078 mmol, 94.3%); R_f = 0.20 (CHCl₃–hexane, 7:3). IR (ATR): 3453, 3301, 2964, 2874, 2360, 1698, 1658, 1593, 1537, 1460, 1415, 1314, 1264, 1201, 1071, 988, 850, 809, 744 cm^–1. ¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 9.08 (s, 1 H, perylene ArH), 8.79 (d, J = 9.6 Hz, 1 H, perylene ArH), 8.60–8.72 (m, 3 H, perylene ArH), 8.36 (s, 1 H, perylene ArH), 5.03–5.11 (m, 2 H, ethylpropyl), 4.49 (t, J = 9.6 Hz, 2 H, –OCH₂), 2.81 (td, J = 9.6, 3.2 Hz, 2 H, –CH₂), 2.19–2.34 (m, 4 H, ethylpropyl), 1.87–2.01 (m, 5 H, merged –CH + ethylpropyl), 0.90–0.96 (m, 12 H, ethylpropyl). ¹³C NMR (125 MHz, CDCl₃): δ = 11.26, 11.28, 24.89, 25.01, 29.71, 57.94, 58.08, 58.23, 58.38, 128.83, 129.00, 129.55, 129.82, 131.29, 131.54, 141.03, 147.65, 147.82. Emission = 540 nm; Absorption = 550 nm (MeCN–H₂O with f _w = 50 vol%).
• 29 PDI 4Dark-blue solid; yield: 54.2 mg (0.079 mmol, 94.3%); R_f = 0.27 (CHCl₃–hexane, 7:3). IR (ATR): 3452, 3301, 3061, 2961, 2926, 2873, 2360, 1702, 1662, 1597, 1541, 1459, 1419, 1344, 1314, 1268, 1201, 1073, 1004, 926, 810, 742, 652 cm^–1. ¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 9.15 (s, 1 H, perylene ArH), 8.85 (s, 1 H, perylene ArH), 8.54 (d, J = 8.0 Hz, 1 H, perylene ArH), 8.39 (s, 1 H, perylene ArH), 8.30 (d, J = 8.0 Hz, 1 H, perylene ArH), 5.00–5.10 (m, 2 H, ethylpropyl), 4.53 (t, J = 7.2 Hz, 2 H, –OCH₂), 2.81 (td, J = 7.2, 2.4 Hz, 2 H, –CH₂), 2.19–2.30 (m, 4 H, ethylpropyl), 1.99 (t, J = 2.8 Hz, 1 H, –CH), 1.89–1.98 (m, 4 H, ethylpropyl), 0.90–0.95 (m, 12 H, ethylpropyl). ¹³C NMR (125 MHz, CDCl₃): δ = 11.26, 11.32, 18.94, 24.86, 25.04, 58.36, 58.63, 68.04, 71.02, 78.76, 116.01, 123.54, 126.60, 127.53, 129.64, 129.80, 148.03, 159.02. Emission = 541 nm; Absorption = 565 nm (MeCN–H₂O with f _w = 50 vol%).
• 30 PDI 5Brownish-red liquid; yield: 102.1 mg (0.15 mmol, 95.2%); R_f = 0.23 (CHCl₃–hexane, 7:3). ¹H NMR (500 MHz, CDCl₃, 25 °C): δ = 10.15 (s, 1 H, CHO), 8.82 (s, 1 H, perylene ArH), 8.66 (t, J = 10.0 Hz, 2 H, perylene ArH), 8.24 (d, J = 10.0 Hz, 2 H, perylene-ArH), 8.06 (d, J = 10.0 Hz, 2 H, ArH), 7.82 (d, J = 10.0 Hz, 1 H, perylene ArH), 7.74 (d, J = 10.0 Hz, 1 H, ArH), 7.66 (d, J = 10.0 Hz, 1 H, ArH), 5.01–5.06 (m, 2 H, ethylpropyl), 2.19–2.28 (m, 4 H, ethylpropyl), 1.88–1.96 (m, 4 H, ethylpropyl), 0.87–0.94 (m, 12 H, ethylpropyl). ¹³C NMR (125 MHz, CDCl₃): δ = 191.2, 147.9, 147.7, 141.0, 136.4, 134.9, 131.6, 131.3, 129.9, 129.6, 129.0, 128.9, 128.1, 58.4, 58.3, 58.1, 58.0, 36.9, 29.7, 25.0, 24.9, 19.2, 11.3, 11.3.
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