Synthesis and Electronic Properties of a Conjugated TTFAQ Trimer and Donor-Acceptor Ensembles of TTFAQ and Anthraquinone

Abstract

We report the first synthesis of a conjugated TTFAQ trimer as well as two TTFAQ-anthraquinone based donor-acceptor ensembles using Sonogashira and Horner-Wadsworth-Emmons reactions. Electronic absorption and electrochemical redox properties of these compounds are described.

extended-tetrathiafulvalene - donor-acceptor - cross-coupling - olefination, heterocycles

References and Notes

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10

Synthesis of 13: To a 100 mL round-bottom flask were added 11b (0.50 g, 0.82 mmol), 8 (0.70 g, 2.1 mmol), anhyd THF (20 mL) and Et₃N (10 mL). The mixture was subjected to rigorous degassing through three freeze-pump-thaw cycles. Under N₂ protection, PdCl₂(PPh₃)₂ (0.040g, 0.057 mmol) and CuI (0.020g, 0.11 mol) were added. The solution was stirred at r.t. overnight. The solvent was removed in vacuo, and the residue was dissolved in CH₂Cl₂, then washed with HCl (1 M) and brine. The organic layer was dried with MgSO₄ and concentrated in vacuo, affording crude product of 13. The crude compound was purified by flash column chromatography over silica gel (CH₂Cl₂-hexanes, 2:1) to give pure 13 (0.42 g, 0.41 mmol, 50%) as a dark brown solid; mp >300 °C (dec.). ¹H NMR (500 MHz, CDCl₃): δ = 8.48 (s, 2 H), 8.36 (m, 6 H), 7.96 (d, J = 8.0 Hz, 2 H), 7.84 (m, 4 H), 7.75 (s, 2 H), 7.62 (d, J = 8.5 Hz, 2 H), 7.55 (d, J = 8.0 Hz, 2 H), 2.442 (s, 6 H), 2.435 (s, 6 H). ¹³C NMR (125 MHz, CDCl₃): δ = 182.8, 182.6, 136.8, 135.4, 134.9, 134.5, 134.4, 134.3, 133.8, 133.7, 133.6, 132.6, 130.5, 130.2, 129.7, 128.6, 127.6, 127.54, 127.50, 126.9, 126.1, 125.8, 122.1, 120.4, 94.5, 89.1, 19.5, 19.3. MALDI-TOF MS: m/z [M + H]⁺ calcd for C₅₆H₃₃O₄S₈: 1025.01; found: 1025.37. IR (neat): 3065, 2919, 2850, 2205, 1723, 1674, 1591 cm^-1.

11

Synthesis of 14: To a 50 mL round-bottom flask were added anhyd THF (10 mL), 10 (0.076 g, 0.25 mmol), and n-BuLi (1.38 M in hexane, 0.18 mL, 0.25 mmol) at -78 °C, and the solution was stirred for 30 min. Compound 13 (0.050 g, 0.049 mmol) was then added slowly at -78 °C. The solution was allowed to warm up to r.t. and then stirred overnight. The solvent was removed in vacuo, and the residue was dissolved in CH₂Cl₂, then washed with HCl (1 M) and sat. brine. The organic layer was dried with MgSO₄ and concentrated in vacuo, affording crude product of 14. The crude compound was purified by flash column chromatography over silica gel (CHCl₃) to give pure 14 (0.076 g, 0.044 mmol, 90%) as an orange solid; mp >300 °C (dec). ¹H NMR (500 MHz, CDCl₃): δ = 7.73 (s, 4 H), 7.57 (m, 8 H), 7.51 (m, 4 H), 7.33 (m, 4 H), 2.44 (m, 36 H). Meaningful ¹³C NMR spectrum could not be obtained due to low solubility. MALDI-TOF MS: m/z [M + H]⁺ calcd for C₇₆H₅₇S₂₄: 1736.77; found: 1736.56. IR (neat): 3052, 2917, 2849, 1670, 1528, 1493 cm^-1.

12

Synthesis of 15: To a 100 mL round-bottom flask were added 12b (0.078 g, 0.13 mmol), 5 (0.015 g, 0.033 mmol), THF (15 mL), and Et₃N (15 mL). The mixture was subjected to rigorous degassing through three freeze-pump-thaw cycles. Under N₂ protection, Pd(PPh₃)₄ (0.040 g, 0.035 mmol) and CuI (0.020 g, 0.11 mol) were added. The solution was stirred at r.t. overnight. The solvent was removed in vacuo, and the residue was dissolved in CH₂Cl₂, then washed with HCl (1 M) and sat. brine. The organic layer was dried with MgSO₄ and concentrated in vacuo, affording crude product of 15. The crude compound was purified by flash column chromatography over silica gel (CH₂Cl₂-hexanes, 1:1) to give pure 15 (0.035 g, 0.025 mmol, 76%) as a dark brown solid; mp >250 °C (dec). ¹H NMR (500 MHz, CDCl₃): δ = 8.48 (s, 2 H), 8.34 (d, J = 8.0 Hz, 2 H), 7.96 (d, J = 8.0 Hz, 2 H), 7.74 (s, 2 H), 7.59 (m, 6 H), 7.52 (d, J = 8.0 Hz, 2 H), 7.34 (m, 4 H), 2.43 (s, 6 H), 2.42 (s, 6 H), 2.412 (s, 6 H), 2.406 (s, 6 H). Meaningful ¹³C NMR spectrum could not be obtained due to low solubility. MALDI-TOF MS: m/z [M + H]⁺ calcd for C₆₆H₄₅O₂S₁₆: 1380.90; found: 1382.63. IR (neat): 3059, 2918, 2850, 2206, 1724, 1674, 1591 cm^-1.

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15 Bryce MR. de Miguel P. Devonport W. Chem. Commun.  1998,  2565 

16

The exact origins of the irreversible peaks are not clear and await further investigations. At this juncture, they are tentatively attributed to complex electrode reactions subsequent to the oxidation of 14.