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DOI: 10.1055/s-2008-1078571
Synthesis, Characterization, and Photoluminescence of Thiophene-Containing Spiro Compounds
Publication History
Publication Date:
02 July 2008 (online)
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Abstract
Spiro[fluorene-9,4′-[4H]indeno[3,2-b]thiophene] (spiro-FIT) and bis(spiro-FIT)arenes were synthesized. The UV/vis spectra, emission spectra, and cyclic voltammetry of these compounds are described.
Key words
spiro compounds - Stille reaction - heterocycles - cross-coupling - chromophores
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6a
(a) Preparation of Spiro[fluorene-9,4′-[4 H ]indeno[3,2- b ]thiophene] (spiro-FIT)
To an AcOH solution (30 mL) of 9-(2-thienylphenyl)-fluoren-9-ol (1, 390 mg, 1.14 mmol) was added concentrated HCl (1 mL) at r.t., and the mixture was stirred for 1 h. After the addition of H2O (30 mL), precipitate was collected, washed with H2O, and dissolved in CH2Cl2. The CH2Cl2 solution was washed with 5% aq NaHCO3 and brine. The organic layer was dried over MgSO4 and filtered. The solvents were evaporated, and the residue was purified with column chromatography on SiO2 (EtOAc-hexane, 1:50) to give spiro-FIT (352 mg, 96%) as a white solid; mp 167.0-167.3 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 6.47 (d, 1 H, J = 4.7 Hz), 6.63 (d, 1 H, J = 7.3 Hz), 6.80 (d, 2 H, J = 7.3 Hz), 6.98 (dd, 1 H, J = 7.3, 7.7 Hz), 7.12 (dd, 2 H, J = 7.3, 7.7 Hz), 7.22 (d, 1 H, J = 4.8 Hz), 7.28 (dd, 1 H, J = 7.3, 7.7 Hz), 7.36 (dd, 2 H, J = 7.3, 7.3 Hz), 7.53 (d, 1 H, J = 7.3 Hz), 7.82 (d, 2 H, J = 7.7 Hz). ¹³C NMR (75.5 MHz, CDCl3): δ = 63.5, 118.9, 120.0, 121.4, 123.7, 123.8, 125.9, 127.6, 127.7, 127.8, 128.1, 138.6, 141.7, 143.5, 146.8, 151.8, 152.0. Anal. Calcd for C23H14S: C, 85.68; H, 4.38. Found: C, 85.61; H, 4.18. -
6b
(b) Preparation of 2-Bromospiro[fluorene-9,4′-[4 H ]indeno[3,2- b ]thiophene] (Br-spiro-FIT)
To a DMF solution (10 mL) of spiro-FIT (352 mg, 1.09 mmol) was added a solution of NBS (236 mg, 1.31 mmol) in DMF (10 mL) in the dark, and the mixture was stirred at r.t. for 14 h. The reaction mixture was poured into brine, extracted with EtOAc, and washed with brine. The organic layer was dried over MgSO4 and filtered. The solvents were evaporated, and the residue was purified with column chromatography on SiO2 (EtOAc-hexane, 1:50) to give Br-spiro-FIT (333 mg, 76%) as a white solid; mp 183.2-183.7 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 6.48 (s, 1 H), 6.63 (d, 1 H, J = 7.7 Hz), 6.80 (d, 2 H, J = 7.3 Hz), 6.99 (dd, 1 H, J = 7.3, 7.7 Hz), 7.12 (dd, 2 H, J = 7.3, 7.3 Hz), 7.27 (dd, 1 H, J = 7.3, 7.7 Hz), 7.36 (dd, 2 H, J = 7.3, 7.7 Hz), 7.46 (d, 1 H, J = 7.3 Hz), 7.82 (d, 2 H, J = 7.7 Hz). ¹³C NMR (75.5 MHz, CDCl3): δ = 64.1, 114.0, 118.9, 120.1, 123.7, 123.8, 124.5, 126.2, 127.8, 128.0, 138.3, 141.7, 143.6, 146.0, 150.5, 150.9 (one peak cannot be discriminated due to overlap with another peak). Anal. Calcd for C23H13BrS: C, 68.83; H, 3.30. Found: C, 68.59; H, 3.27. -
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(c) Preparation of 2,5-bis{spiro[fluorene-9,4′-[4 H ]indeno[3,2- b ]thiophen-2-yl]}furan (3f)
Sn-spiro-FIT (245 mg, 0.400 mmol), 2,5-dibromofuran (45.1 mg, 0.200 mmol), Pd(PPh3)4 (11.6 mg, 0.0100 mmol), and toluene (2 mL) were added to a dry Schlenk flask under N2. After the mixture was stirred at 110 ˚C for 12 h in the dark, the reaction mixture was cooled, and yellow precipitate was filtered. The precipitate was washed with Et2O, dissolved in THF, and filtered by Florisil. The solvents were evaporated to give 3f (117 mg, 82%) as a yellow solid; mp >300 ˚C. ¹H NMR (300 MHz, CDCl3): δ = 6.39 (s, 2 H), 6.61-6.63 (m, 4 H), 6.82 (d, 4 H, J = 7.7 Hz), 6.97 (dd, 2 H, J = 6.6, 7.7 Hz), 7.12 (dd, 4 H, J = 6.6, 7.3 Hz), 7.28 (dd, 2 H, J = 6.6, 7.3 Hz), 7.37 (dd, 4 H, J = 6.6, 7.3 Hz), 7.48 (d, 2 H, J = 7.7 Hz), 7.83 (d, 4 H, J = 7.7 Hz). ¹³C NMR (75.5 MHz, CDCl3): δ = 63.7, 107.2, 116.7, 118.8, 120.1, 123.6, 123.8, 126.1, 127.8, 127.9, 136.0, 138.4, 141.7, 142.2, 146.4, 148.5, 151.5, 152.6 (one peak cannot be discriminated due to overlap with another peak). Anal. Calcd for C50H28OS2: C, 84.72; H, 3.98. Found: C, 84.45; H, 3.88. -
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