Synthesis and Optical Properties of Donor-Acceptor Tetrakis(phenyl­ethynyl)benzenes

Abstract

A simple and efficient synthesis of a series of donor-acceptor substituted 1,2,4,5-tetrakis(phenylethynyl)benzenes is described. The molecules constructed exhibit interesting optical properties. Preliminary studies show that the tetraynes hold promise as nonlinear optical (NLO) materials.

Key words

alkynes - arenes - chromophores - cross-coupling - palladium

References

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5

Marsden, J. A.; Miller, J. J.; Haley, M. M., manuscript in preparation.

10

General Alkyne Coupling Procedure. A solution of haloarene (1 equiv) in i-Pr₂NH-THF (3:1, 0.05 M) was degassed by bubbling Ar for 20 min or by three freeze-pump-thaw cycles. Pd(PPh₃)₂Cl₂ (for iodoarene) or Pd(PPh₃)₄ (for bromoarene) (0.05 equiv) and CuI (0.12 equiv) were added and the flask was sealed under Ar. The terminal acetylene (1.1 equiv per halide) was then added via syringe, and the reaction mixture stirred at r.t. (for iodoarenes) or 40 °C (for bromoarenes) for 12 h. Upon completion, the reaction mixture was concentrated in vacuo, diluted with CH₂Cl₂, and filtered through a bed of silica gel. The filtrate was concentrated, and the crude material was purified by column chromatography on silica gel (hexanes-CH₂Cl₂).
4: ¹H NMR (CDCl₃): δ = 0.98 (t, J = 7.4 Hz, 24 H), 1.37 (sext, J = 7.5 Hz, 16 H), 1.59 (quin, J = 7.7 Hz, 16 H), 3.30 (t, J = 7.7 Hz, 16 H), 6.59 (d, J = 9.2 Hz, 8 H), 7.43 (d, J = 9.2 Hz, 8 H), 7.63 (s, 2 H). ¹³C NMR (CDCl₃): δ = 13.96, 20.29, 29.36, 50.66, 86.31, 96.23, 108.97, 111.14, 124.60, 133.05, 133.88, 147.98.
5: ¹H NMR (CDCl₃): δ = 0.97 (t, J = 7.4 Hz, 8 H), 1.37 (sext, J = 7.4 Hz, 8 H), 1.59 (quin, J = 8.4 Hz, 8 H), 3.31 (t, J = 7.7 Hz, 12 H), 6.59 (d, J = 9.3 Hz, 4 H), 7.42 (d, J = 9.0 Hz, 4 H), 7.67 (d, J = 8.9 Hz, 4 H) 7.73 (s, 2 H), 8.24 (d, J = 8.9 Hz, 4 H). ¹³C NMR (CDCl₃): δ = 13.98, 20.30, 29.32, 50.65, 86.12, 92.65, 92.80, 98.49, 108.06, 111.07, 122.66, 123.70, 126.91, 129.90, 132.20, 133.18, 134.65, 146.99, 148.37.
6: ¹H NMR (CDCl₃): δ = 0.98 (t, J = 7.4 Hz, 8 H), 1.38 (sext, J = 7.5 Hz, 8 H), 1.58 (quin, J = 7.9 Hz, 8 H), 3.30 (t, J = 7.7 Hz, 12 H), 6.57 (d, J = 9.0 Hz, 4 H), 7.35 (d, J = 9.0 Hz, 4 H), 7.66 (d, J = 9.0 Hz, 4 H) 7.66 (s, 1 H), 7.68 (s, 1 H), 8.18 (d, J = 9.0 Hz, 4 H). ¹³C NMR (CDCl₃): δ = 13.98, 20.30, 29.32, 50.65, 85.76, 92.55, 93.35, 98.87, 107.77, 111.14, 122.06, 123.64, 127.85, 130.18, 132.25, 133.12, 134.00, 135.20, 146.93, 148.50.
7: ¹H NMR (CDCl₃): δ = 0.97 (t, J = 7.4 Hz, 8 H), 1.37 (sext, J = 7.5 Hz, 8 H), 1.57 (quin, J = 7.8 Hz, 8 H), 3.31 (t, J = 7.7 Hz, 12 H), 6.59 (d, J = 9.0 Hz, 4 H), 7.35 (d, J = 9.0 Hz, 4 H), 7.71 (d, J = 9.0 Hz, 4 H) 7.72 (s, 2 H), 8.23 (d, J = 9.0 Hz, 4 H). ¹³C NMR (CDCl₃): δ = 13.95, 20.25, 29.30, 50.60, 85.49, 92.92, 93.27, 98.10, 107.84, 111.10, 123.58, 124.09, 125.74, 130.05, 132.32, 132.99, 134.55, 146.95, 148.37.
8: ¹H NMR (CDCl₃): δ = 0.98 (t, J = 7.2 Hz, 8 H), 1.38 (sext, J = 7.5 Hz, 8 H), 1.59 (quin, J = 8.2 Hz, 8 H), 3.31 (t, J = 7.7 Hz, 12 H), 6.59 (d, J = 9.0 Hz, 4 H), 7.39 (d, J = 9.0 Hz, 4 H), 7.60 (br s, 4 H), 7.66 (d, J = 1.8 Hz, 2 H). ¹³C NMR (CDCl₃): δ = 13.98, 20.28, 29.31, 50.65, 85.95, 91.93, 92.73, 98.35, 108.11, 111.10, 111.67, 118.40, 122.74, 126.76, 127.88, 131.97, 132.10, 133.2, 134.63, 148.30.
9: ¹H NMR (CDCl₃): δ = 0.97 (t, J = 7.4 Hz, 12 H), 1.37 (sext, J = 7.5 Hz, 8 H), 1.59 (quin, J = 7.5 Hz, 8 H), 3.30 (t, J = 7.7 Hz, 8 H), 6.58 (d, J = 8.7 Hz, 4 H), 7.36 (d, J = 8.7 Hz, 4 H), 7.65 (s, 4 H), 7.69 (s, 1 H) 7.71 (s, 1 H). ¹³C NMR (CDCl₃): δ = 14.00, 20.31, 29.33, 50.66, 85.63, 92.36, 92.72, 98.65, 107.78, 111.15, 111.55, 118.56, 122.24, 127.67, 128.17, 132.11, 133.12, 134.04, 135.08, 148.45.
10: ¹H NMR (CDCl₃): δ = 0.97 (t, J = 7.4 Hz, 12 H), 1.38 (sext, J = 7.8 Hz, 4 H), 1.58 (quin, J = 7.7 Hz, 4 H), 3.31 (t, J = 7.7 Hz, 4 H), 6.58 (d, J = 9.0 Hz, 4 H), 7.35 (d, J = 9.0 Hz, 4 H), 7.65 (s, 8 H), 7.70 (s, 2 H). ¹³C NMR (CDCl₃): δ = 13.86, 18.84, 20.17, 29.21, 47.06, 50.54, 54.62, 85.29, 92.20, 92.99, 97.89, 107.74, 111.06, 111.55, 118.40, 124.07, 125.63, 127.96, 131.97, 132.04, 132.89, 134.44, 148.29.
15: ¹H NMR (CDCl₃): δ = 0.26 (s, 18 H), 7.69 (s, 2 H). ¹³C NMR (CDCl₃): δ = -0.16, 100.84, 100.05, 124.46, 126.05, 136.54.
16: ¹H NMR (CDCl₃): δ = 0.27 (s, 18 H), 1.13 (s, 63 H), 7.53 (s, 2 H). ¹³C NMR (CDCl₃): δ = -0.04, 11.29, 18.75, 97.46, 100.60, 102.11, 104.22, 125.10, 125.16, 137.02.
17: ¹H NMR (CDCl₃): δ = 0.96 (t, J = 7.4 Hz, 8 H), 1.14 (s, 42 H), 1.36 (sext, J = 7.4 Hz, 8 H), 1.58 (quin, J = 7.6 Hz, 8 H), 3.29 (t, J = 7.5 Hz, 12 H), 6.57 (d, J = 9.0 Hz, 4 H), 7.41 (d, J = 9.0 Hz, 4 H), 7.57 (s, 2 H). ¹³C NMR (CDCl₃): δ = 11.32, 13.98, 18.77, 20.31, 29.36, 50.66, 85.97, 96.06, 97.11, 104.98, 108.56, 111.14, 123.76, 125.72, 133.16, 135.95, 148.17.

14

Slepkov, A. D.; Hegmann, F. A.; Marsden, J. A.; Miller, J. J.; Haley, M. M.; Tykwinski, R. R., work in progress.