Synlett 2025; 36(05): 576-580
Synthesis of Bifluorenylidene- and Cycloocta[1,2,3-jk :6,5,4-j ′k ′]difluorene-Extended Tetrathiafulvalenes: Novel Multi-Redox Systems
Jonathan Kirschner Solberg Hansen
,
Mogens Brøndsted Nielsen∗
The Novo Nordisk Foundation is acknowledged for financially supporting this work (grant #NNF20OC0061574).
Abstract
Herein, we present the synthesis of a novel 9,9′-bifluorenylidene-extended tetrathiafulvalene (TTF) as an E /Z isomeric mixture that was found to readily undergo an oxidative dimerization to furnish a TTF vinylogue with the two dithiafulvene units connected to an eight-membered ring fused to a bifluorenylidene core. This compound exhibited multiredox behavior and was found to take six charge states under cyclic voltammetry conditions: –2, –1, 0, +1, +2, +3. The dication corresponds to a cycloocta[1,2,3-jk :6,5,4-j ′k ′]difluorene with two appended 1,3-dithiolium rings.
Key words
bifluorenylidene -
C–C bond formation -
chromophores -
olefination -
polycyclic aromatic hydrocarbons -
tetrathiafulvalenes
Supporting Information
Supporting information for this article is available online at https://doi.org/10.1055/a-2373-0422.
Supporting Information
Publication History
Received: 15 June 2024
© 2024. Thieme. All rights reserved
Georg Thieme Verlag KG
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(E/Z )-4
Phosphonate 12 (575.6 mg, 1.731 mmol) was added to a 50-mL Schlenk flask containing dry THF (10 mL). Dialdehyde 11 (166.0 mg, 431.8 μmol) was added to a second 100-mL Schlenk flask containing dry THF (25 mL). Both flasks were cooled to –78 °C, and a 1 M solution of LiHMDS in toluene (1.7 mL, 1.7 mmol) was slowly added to the flask containing 12 , resulting in a bright-yellow coloration. The contents of the two flasks were stirred for 20 min, before the contents of the flask containing the deprotonated phosphonate 12 were cannulated into the second flask. The resulting mixture was allowed to reach rt for 20 h, and the reaction was then quenched by washing with sat. aq NH4 Cl (50 mL). The two phases were separated, and the aqueous phase was extracted with CH2 Cl2 (2 × 30 mL). The combined organic phases were dried (MgSO4 ), filtered, and concentrated in vacuo. The residue was purified by flash column chromatography [silica gel, CH2 Cl2 –heptane (2:3)] to give a mixture of the E /Z isomers as a dark blackish-green powder; yield: 128.3 mg (37%; E /Z = 5:1); Rf
= 0.31 (CH2 Cl2 –heptane, 2:3).
IR (ATR, film): 3046.5w, 2973.1m, 2921.8m, 2865.7w, 1667.7w, 1561.0s, 1492.3m, 1444.2s, 1420.4w, 1402.0m, 1373.7w, 1350.0w, 1258.5m, 1055.1w, 966.1w, 889.8w, 813.0m, 781.7w, 765.3s, 749.0s, 738.2m, 605.6w cm–1 . HRMS (MALDI-FT-ICR): m /z [M•+ ] Calcd for C42 H36 S8 : 796.05827; found: 796.05412.
(E )-4
1 H NMR (500 MHz, CD2 Cl2 ): δ = 7.72–7.68 (m, 4 H), 7.49 (dd, J = 7.6, 7.6 Hz, 2 H), 7.42 (d, J = 7.8 Hz, 2 H,), 7.25–7.19 (m, 2 H), 7.06 (ddd, J = 7.4, 7.0, 1.2 Hz, 2 H), 7.01 (d, J = 7.8 Hz, 2 H), 6.04 (s, 2 H), 2.98–2.59 (m, 8 H), 1.37 (t, J = 7.3 Hz, 6 H), 1.20 (t, J = 7.3 Hz, 6 H). 13 C NMR (126 MHz, CD2 Cl2 ): δ = 142.76, 140.56, 139.40, 138.70, 136.03, 135.69, 134.51, 129.70, 128.51, 128.38, 128.24, 126.85, 125.69, 124.85, 119.57, 118.77, 118.40, 30.79, 30.61, 15.44, 15.38.
(Z )-4
1 H NMR (500 MHz, CD2 Cl2 ): δ = 8.42 (d, J = 7.9 Hz, 2 H), 7.75 (d, J = 7.5 Hz, 2 H), 7.64 (dd, J = 7.4, 1.0 Hz, 2 H), 7.47–7.44 (m, 2 H), 7.31 (ddd, J = 7.4, 7.4, 1.0 Hz, 2 H), 7.25–7.19 (m, 4 H), 5.45 (s, 2 H), 2.98–2.59 (m, 8 H), 1.33–1.23 (m, 12 H). 13 C NMR (126 MHz, CD2 Cl2 ): δ = 141.59, 141.39, 140.10, 139.75, 134.99, 134.57, 134.27, 129.54, 128.72, 127.32, 127.03, 125.40, 120.23, 117.87, 114.68, 30.83, 15.52, 15.25.
11
5 : I2 (35.5 mg) was added to a solution of compound 4 (E/Z ) (41.3 mg, 51.1 μmol) in CH2 Cl2 (10 mL), and the mixture was stirred for 5 min. The reaction was then quenched with sat. aq Na2 S2 O3 (25 mL), and the mixture was stirred for another 5 min. The two phases were separated, and the aqueous phase was extracted with CH2 Cl2 (10 mL). The combined organic phases were dried (MgSO4 ), filtered, and concentrated in vacuo. The residue was purified by column chromatography [silica gel, CH2 Cl2 –heptane (3:2)] to give a black–yellow powder; yield: 14.3 mg (35%); Rf
= 0.45 (CH2 Cl2 –heptane, 1:1). IR (ATR, film): 3047.92, 2957.0m, 2922.0s, 2852.8m, 1597.3w, 1563.0m, 1534.6m, 1487.9m, 1444.1m, 1419.8m, 1400.4m, 1374.2m, 1349.0m, 1257.5m, 1053.9w, 965.9w, 886.4w, 767.6s, 752.4s, 736.8m, 705.9m, 662.3w, 609.3w, 582.8w, 468.6w cm–1 . 1 H NMR (500 MHz, CD2 Cl2 ): δ = 8.14 (d, J = 8.0 Hz, 2 H), 7.79 (dd, J = 7.6, 1.2 Hz, 2 H), 7.76 (dd, J = 7.5, 1.2 Hz, 2 H), 7.73 (d, J = 7.5 Hz, 2 H), 7.43 (dd, J = 7.5, 7.5 Hz, 2 H), 7.28 (ddd, J = 7.5, 7.4, 1.0 Hz, 2 H), 7.03 (ddd, J = 7.6, 7.2, 1.2 Hz, 2 H), 2.73 (q, J = 7.3 Hz, 4 H), 2.67 (q, J = 7.4 Hz, 4 H), 1.18 (t, J = 7.4 Hz, 6 H), 1.14 (t, J = 7.3 Hz, 6 H). 13 C NMR (126 MHz, C6 D6 ): δ = 142.52, 141.06, 140.75, 139.36, 139.01, 138.23, 135.82, 129.98, 129.71, 129.07, 128.57, 127.67, 127.51, 127.35, 126.15, 119.76, 119.63, 30.63, 30.61, 15.27, 15.25. HRMS (MALDI-FT-ICR): m /z [M•+ ] Calcd for C42 H34 S8 : 794.04207; found: 794.04303
12
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