Synthesis, Characterization, and Photoluminescence of Thiophene-Containing Spiro Compounds

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

References and Notes

• 1a Perepichka IF. Perepichka DF. Meng H. Wudl F. Adv. Mater.  2005,  17:  2281 
• 1b Fichou D. J. Mater. Chem.  2000,  10:  571 
• 1c Murphy AR. Fréchet JMJ. Chem. Rev.  2007,  107:  1066 
• 2a Mushrush M. Facchetti A. Lefenfeld M. Katz HE. Marks TJ. J. Am. Chem. Soc.  2003,  125:  9414 
• 2b Dingemans TJ. Bacher A. Thelakkat M. Pedersen LG. Samulski ET. Schmidt H.-W. Synth. Met.  1999,  105:  171 
• 2c Hotta S. Ichino Y. Yoshida Y. Yoshida M. J. Phys. Chem. B  2000,  104:  10316 
• 2d Lee SA. Hotta S. Nakanishi F. J. Phys. Chem. A  2000,  104:  1827 
• 2e Ohsedo Y. Yamate T. Okumoto K. Shirota Y. J. Photopolym. Sci. Technol.  2001,  14:  297 
• 2f Kojima T. Nishida J. Tokito S. Yamashita Y. Chem. Lett.  2007,  36:  1198 
• 3 Aldred MP. Vlachos P. Contoret AEA. Farrar SR. Chung-Tsoi W. Mansoor B. Woon KL. Hudson R. Kelly SM. O’Neill M. J. Mater. Chem.  2005,  15:  3208 
• 4a Saragi TPI. Spehr T. Siebert A. Fuhrmann-Lieker T. Salbeck J. Chem. Rev.  2007,  107:  1011 
• 4b Walzer K. Maennig B. Pfeiffer M. Leo K. Chem. Rev.  2007,  107:  1233 
• 4c Luo J. Zhou Y. Niu Z.-Q. Zhou Q.-F. Ma Y. Pei J. J. Am. Chem. Soc.  2007,  129:  11314 
• 4d Takagi K. Momiyama M. Ohta J. Yuki Y. Matsuoka S. Suzuki M. Macromolecules  2007,  40:  8807 
• 5a Xie L.-H. Fu T. Hou X.-Y. Tang C. Hua Y.-R. Wang R.-J. Fan Q.-L. Peng B. Wei W. Huang W. Tetrahedron Lett.  2006,  47:  6421 
• 5b Mitschke U. Bäuerle P. J. Chem. Soc., Perkin Trans. 1  2001,  740 
• 5c Ong T.-T. Ng S.-C. Chan HSO. Vardhanan RV. Kumura K. Mazaki Y. Kobayashi K. J. Mater. Chem.  2003,  13:  2185 
• 5d Xie L.-H. Hou X.-Y. Hua Y.-R. Huang Y.-Q. Zhao B.-M. Liu F. Peng B. Wei W. Huang W. Org. Lett.  2007,  9:  1619 
• Representative Experimental Procedures
• 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.

• 6c

  (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.

• 7a Turbiez M. Frère P. Roncali J. J. Org. Chem.  2003,  68:  5357 
• 7b Takamiya K. Oharuda A. Aso Y. Ogura F. Otsubo T. Chem. Mater.  2000,  12:  2196 
• 8a Apperloo JJ. Groenendaal LB. Verheyen H. Jayakannan M. Janssen RAJ. Dkhissi A. Beljonne D. Lazzaroni R. Brédas J.-L. Chem. Eur. J.  2002,  8:  2384 
• 8b Yokooji A. Satoh T. Miura M. Nomura M. Tetrahedron  2004,  60:  6757