Electron Acceptors Based on Cyclopentannulated Tetracenes

Published as part of the Cluster Synthesis of Materials

Abstract

New cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs) based on tetracene have been prepared by a palladium-catalyzed cyclopentannulation reaction. The new compounds have low-energy lowest unoccupied molecular orbitals (LUMOs) and relatively small band gaps. The photooxidative stability was intermediate to previously prepared CP-PAHs based on anthracene and pentacene as found in traditional acene stabilities. Scholl cyclodehydrogenation of pendant aryl groups led to materials that quickly formed endoperoxide products.

Key words

cyclopenta-fused polycyclic aromatic hydrocarbons - electron acceptors - acenes - palladium-catalyzed annulation

• References and Notes

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• 26 1,2,7,8-Tetrakis(3-(dodecyloxy)phenyl)dicyclopenta[de,mn]tetracene (6): In a glove box, 4 (0.127 g, 0.328 mmol), 5 (0.430 g, 0.786 mmol), Pd₂(dba)₃ (30.0 mg, 0.0328 mmol), P(o-Tol)₃ (15.1 mg, 0.0495 mmol), KOAc (0.161 g, 1.64 mmol), LiCl (27.8 mg, 0.657 mmol) and DMF (7.67 mL) were combined in a sealed tube and stirred overnight at 130 °C. The reaction mixture was cooled to room temperature and poured dropwise into methanol (50 mL) and filtered. The solid was washed with methanol and acetone to give 5 (0.164 g, 25.0%) as a green solid. ¹H NMR (500 MHz, CD₂Cl₂): δ = 8.62 (s, 2 H), 7.87 (d, J = 6.5 Hz, 2 H), 7.73 (d, J = 8.5 Hz, 2 H), 7.57 (dd, J = 8.4, 6.6 Hz, 2 H), 7.50 (t, J = 7.7 Hz, 2 H), 7.29 (t, J = 7.9 Hz, 2 H), 7.24 (d, J = 7.4 Hz, 2 H), 7.16 (s, 2 H), 7.13–7.09 (m, 4 H), 6.98 (s, 2 H), 6.84 (dd, J = 8.1, 2.1 Hz, 2 H), 4.00 (t, J = 6.6 Hz, 4 H), 3.83 (t, J = 6.6 Hz, 4 H), 1.80–1.71 (m, 8 H), 1.48–1.19 (m, 72 H), 0.91 (q, J = 7.0 Hz, 12 H). ¹³C NMR (126 MHz, CD₂Cl₂): δ = 159.38, 158.92, 141.12, 139.74, 139.39, 136.67, 136.33, 136.08, 131.06, 129.60, 129.00, 128.89, 127.69, 126.93, 126.68, 125.64, 124.20, 122.93, 122.43, 116.58, 115.65, 114.27, 113.69, 68.15, 67.93, 31.93, 31.91, 29.71, 29.65, 29.60, 29.41, 29.38, 29.35, 29.22, 29.16, 26.01, 22.70, 22.68, 13.88. HRMS: m/z calcd for C₉₄H₁₂₄O₄: 1316.9500; found: 1316.9111. 4,4′,4′′,4′′′-(Dicyclopenta[de,mn]tetracene-1,2,7,8-tetrayl)tetrakis(2-methylthiophene) (8): In a glove box, 4 (41.3 mg, 0.107 mmol), 7 (56.0 mg, 0.257 mmol), Pd₂(dba)₃ (9.80 mg, 0.0107 mmol), P(o-Tol)3 (4.92 mg, 0.0162 mmol), KOAc (52.6 mg, 0.536 mmol), LiCl (9.12 mg, 0.215 mmol) and DMF (10.7 mL) were combined in a sealed tube and stirred overnight at 130 °C. The reaction mixture was cooled to room temperature and poured dropwise into methanol (50 mL) and filtered. The solid was washed with methanol and acetone to give 7 (20.2 mg, 28.3%) as a green solid. ¹H NMR (500 MHz, CD₂Cl₂): δ = 8.47 (s, 2 H), 7.84 (d, J = 6.5 Hz, 2 H), 7.67 (d, J = 8.5 Hz, 2 H), 7.47 (dd, J = 8.4, 6.6 Hz, 2 H), 7.10 (d, J = 1.1 Hz, 2 H), 7.04 (d, J = 1.1 Hz, 2 H), 6.91 (s, 2 H), 6.76 (s, 2 H), 2.59 (s, 6 H), 2.40 (s, 6 H). ¹³C NMR (126 MHz, CD₂Cl₂): δ = 140.67, 139.63, 139.20, 137.89, 136.50, 135.69, 135.64, 132.68, 130.89, 128.97, 128.03, 127.55, 126.92, 126.90, 126.34, 125.12, 124.11, 122.34, 121.46, 15.27, 15.09. HRMS: m/z calcd for C₄₂H₂₈S₄: 660.1074; found: 659.926.
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• 28 Unpublished results.