Synthesis and Characterization of 2-Alkylbenzotriazole-Based Donor-π-Acceptor-Type Copolymers

Abstract

Four donor-π-acceptor-type copolymers were synthesized via palladium-catalyzed Sonogashira coupling reaction. The resulting donor-π-acceptor-conjugated copolymers can show fluorescence emission in the range of λ = 473–568 nm, and the band gaps of the alternating polymers can be tuned in the range 3.09–3.74 eV by using four different donors.

Key words

donor-π-acceptor - conjugated copolymers - benzotriazoles - fluorescence

• References and Notes

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• 14 Synthesis Procedures for the BTA-Based Conjugated Polymers
  Synthesis of P1 To a 100 mL Schlenk flask, M-1 (0.14 g, 0.05 mmol), M2 (0.31 g, 0.05 mmol), Pd(PPh₃)₄ (2.9 mg, 0.03 mmol), and CuI (0. 5 mg, 0.003 mmol) were added in 10 mL THF and Et₃N (6 mL) under N₂ atmosphere. The mixture was stirred at 90 °C for 2 d. The solvent was evaporated under vacuum after the mixture was cooled to r.t. The residue was dissolved and in CH₂Cl₂ (100 mL) and filtered; the filtrate was then concentrated and added to MeOH to precipitate the polymer. The polymer was dried in vacuum to give 210 mg of product in 58% yield. GPC results: M _w = 17240, M _n = 10740, PDI = 1.54. ¹H NMR (300 MHz, CDCl₃): δ = 7.24–7.21 (m, 6 H), 6.69–6.66 (m, 2 H), 3.77–3.76 (m, 4 H), 1.75–0.85 (m, 50 H). Anal. Calcd for (C₄₈H₆₄N₄S)_n: C, 78.85; H, 9.10; N, 7.66; S, 4.39. Found: C, 78.23; H, 9.16; N, 7.84; S, 4.27. Synthesis of P2 P2 was synthesized from monomers M-1 and M-3 in 70% yield by following in the same procedure used for the preparation of P1. GPC results: M _w = 17240, M _n = 10050, PDI = 1.72. ¹H NMR (300 MHz, CDCl₃): δ = 8.45–7.23 (m, 1 H), 8.21–8.19 (m, 2 H), 7.78–7.16 (m, 5 H), 4.80–4.76 (m, 2 H), 4.20–4.06 (m, 2 H), 1.21–0.85 (m, 50 H). Anal. Calcd for (C₄₈H₆₂N₄O₂S)_n: C, 75.55; H, 8.72; N, 7.34; S, 4.20. Found: C, 75.64; H, 8.63; N, 7.17; S, 4.28. Synthesis of P3 P3 was synthesized from monomers M1 and M4 in 73%yield by following the same procedure used for the preparation of P1. GPC results: M _w = 15780, M _n = 12850, PDI = 1.23. ¹H NMR (300 MHz, CDCl₃): δ = 7.80–8.53 (m, 2 H), 7.40–7.28 (m, 2 H), 7.12–6.81 (m, 6 H), 5.21–4.79 (br, 2 H), 3.83–3.81 (br, 2 H), 2.16–0.84 (m, 50 H). Anal. Calcd for: (C₅₆H₆₈N₄S₃)_n: C, 75.29; H, 7.67; N, 6.27; S, 10.77. Found: C, 75.18; H, 7.76; N, 6.12; S, 10.95. Synthesis of P4 P4 was synthesized from monomers M1 and M5 in 73% yield by following the same procedure used for the preparation of P1. GPC results: M _w = 17910, M _n = 10080, PDI = 1.78. ¹H NMR (300 MHz, CDCl₃): δ = 8.34–8.32 (m, 2 H), 7.84–7.83 (m, 2 H), 7.60–6.31 (m, 8 H), 4.80–4.82 (br, 2 H), 4.18–4.17 (br, 2 H), 2.26–0.59 (m, 50 H). Anal. Calcd for (C₅₆H₆₆N₄O₂S₃)_n: C, 72.69; H, 7.41; N, 6.05; O, 3.46; S, 10.40. Found: C, 72.76; H, 7.36; N, 6.01; O, 3.49; S, 10.37.