Synthesis, Structure, and Properties of Quinone Methides Incorporating Thiophene and Bithiophene Derivatives: New Overcrowded Extended Quinonoid π-Systems

Abstract

The title compounds were synthesized through multiple Suzuki–Miyaura couplings followed by oxidation, and their structures and properties are described. They show large conformational changes and three color change upon electronic reduction.

Key words

quinone methide - thiophene - nonplanar π-system - redox system - electrochromism - Suzuki–Miyaura coupling

• References and Notes

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• 7 Tetrakis(4-hydroxy-3,5-di-tert-butylphenyl)thiophene (5) Colorless crystals; mp 206–207 °C (decomp.). ¹H NMR (400 MHz, CDCl₃): δ = 7.09 (s, 4 H), 6.66 (s, 4 H), 5.08 (s, 2 H), 4.92 (s, 2 H), 1.28 (s, 36 H), 1.18 (s, 36 H). ¹³C NMR (75 MHz, CDCl₃): δ = 152.76, 151.83, 139.99, 137.14, 135.40, 135.14, 128.51, 127.61, 126.18, 125.94, 34.20, 34.06, 30.36, 30.20. MS (MALDI): m/z = 901.0 [M⁺], 902.0 [M + 1]⁺. IR (KBr): ν = 3644 (s), 2957 (s), 2915 (m), 2872 (m), 1433 (s), 1391 (w), 1361 (m), 1313 (m), 1234 (s), 1205 (w), 1156 (s), 1120 (m), 887 (m), 768 (m) cm⁻¹. UV-vis (CH₂Cl₂): λ_max (log ε) = 332 (4.17), 284 (4.30), 246 (4.43), 228 (4.55) nm. Anal. Calcd for C₆₀H₈₄O₄S: C, 79.95; H, 9.39. Found: C, 79.75; H, 9.57. Tetrakis(4-oxo-3,5-di-tert-butylcyclohexa-2,5-dien-1-ylidene)tetrahydrothiophene (3) Dark-purple crystals; mp 246–248 °C (decomp.). ¹H NMR (400 MHz, CDCl₃): δ = 7.20 (d, J = 2.4 Hz, 2 H), 7.20 (d, J = 2.4 Hz, 2 H), 7.13 (d, J = 2.4 Hz), 7.12 (d, J = 2.4 Hz, 2 H), 1.37 (s, 18 H), 1.25 (s, 18 H), 1.24 (s, 18 H), 1.23 (s, 18 H). ¹³C NMR (100 MHz, CDCl₃): δ = 186.42, 185.82, 151.16, 151.14, 150.24, 147.59, 140.75, 140.58, 129.44, 129.25, 128.53, 128.01, 127.75, 127.12, 35.86, 35.83, 35.77, 35.33, 29.54, 29.43, 29.32. MS (MALDI): m/z = 896.9 [M⁺]. IR(KBr) ν = 3003 (w), 2960 (s), 2869 (m), 1625 (s), 1614 (s), 1518 (m), 1485 (w), 1458 (m), 1388 (m), 1362 (s), 1334 (m), 1256 (m), 1124 (m), 1098 (w), 1087 (w), 1028 (w), 930 (w), 904 (m), 880 (w), 849 (m), 820 (w), 798 (w), 744 (w), 695 (w), 664 (w), 650 (w), 531 (w) cm⁻¹. UV-vis (CH₂Cl₂): λ_max (log ε) = 585 (3.58), 456 (4.76), 359 (4.67), 315 (4.45), 259 (4.21) nm. Anal. Calcd for C₆₀H₈₀O₄S: C, 80.31; H, 8.99. Found: C, 79.93; H, 9.04. Hexakis(4-oxo-3,5-di-tert-butylcyclohexa-2,5-dien-1-ylidene)hexahydro-2,2′-bithiophene (4) Green powder; mp 189–191 °C (decomp.). ¹H NMR (400 MHz, CDCl₃): δ = 7.36 (d, J = 2.7 Hz, 2 H), 7.18 (d, J = 2.4 Hz, 2 H), 7.14 (d, J = 2.4 Hz, 2 H), 7.12 (d, J = 2.7 Hz, 2 H), 7.07 (d, J = 2.7 Hz, 2 H), 7.04 (d, J = 2.4 Hz, 2 H), 1.32 (s, 18 H), 1.30 (s, 18 H) 1.28 (s, 18 H), 1.27 (s, 18 H), 1.22 (s, 18 H), 1.21 (s, 18 H). IR (KBr) ν = 3002 (w), 2959 (s), 2870 (w), 1625 (s), 1519 (w), 1485 (m), 1458 (m), 1389 (m), 1363 (s), 1334 (m), 1254 (m), 1127 (m), 1093 (w), 930 (w), 904 (m), 879 (w) cm⁻¹. UV-vis (CH₂Cl₂): λ_max (log ε) = 594 (4.96), 362 (4.20), 308 (3.98), 280 (4.09), 228 (4.41) nm. ESI-HRMS: m/z calcd for C₉₂H₁₂₁O₆S₂: 1385.8599 [M + H]⁺; found: 1385.8530 (because of low solubility of 4, ¹³C NMR spectra were unmeasurable).
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• 10 The DFT calculations were performed at the B3LYP/6-31G* level using Gaussian 03 program. M. J. Frisch et al.; Gaussian 03 (Revision D.01). Gaussian Inc; Wallingford, CT: 2004
• 11 Crystallographic Data C₆₀H₈₀O₄S, M = 897.35, tetragonal, space group I-4c2 (No.120), a = 19.3239(7) Å, c = 29.570(2) Å, V = 11041.8(8) ų, Z = 8, D _calc = 1.080 g cm^–3, F ₀₀₀ = 3904.00, μ = 1.015 cm^–1 (MoKα; λ = 0.71075 Å), 52741 reflections measured, 6340 unique, reflection/parameter ratio = 21.56, R1 = 0.0498 for I> 2σ(I), wR2 = 0.1488 for all data, GOF = 0.878. CCDC 1473992 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 12 Details of crystallographic data, bond lengths, bond angles and torsion angles of 3 are provided in the Supporting Information.
• 13 Each structure of anionic species in Scheme 3 and 4 is represented as the most contributory structure; the radical should be delocalized.
• 14 There is no other spectroscopic evidence for formation of 4⁴⁻ , but it is the most reasonable species judging from such a long-wavelength absorption which is typical for bithiophene-inserted quinoidal structure (ref. 2a) and the cyclic voltammogram of 4.