COMMUNICATIONS
13C NMR: d 12.49, 44.28, 110.92, 112.89, 114.01, 114.84, 115.45, 119.22,
[6] a) K. Clays, A. Persoons, Phys. Rev. Lett. 1991, 66, 2980 ± 2983; K.
Clays, A. Persoons, Rev. Sci. Instrum. 1992, 63, 3285 ± 3289. In contrast
to the coherent frequency doubling in the direction of the laser beam
used in the EFISH method, frequency doubling in the HRS experi-
ment is incoherent and occurs in all directions of space. Problems that
arise from this, like multiphoton fluorescence, have been discovered,
and different methods for its separation or suppression have been
discussed.[1b,d, 8] All HRS results of this work are fluorescence-
corrected; the calibration was done externally against pNA as the
standard.[1b]
128.88, 128.96, 130.63, 131.09, 134.48, 149.66, 153.72.
1-(4-N,N-Diethylaminophenylethynyl)-3,5-diphenyl-2,4,6-tricyanobenzene
(4): Prepared from 11 (221 mg, 0.650 mmol) in analogy to the synthesis of 8;
orange microneedles (215 mg, 0.451 mmol, 69%), m.p. 273 ± 2758C (for-
1
mation of a deep red polymorph at ca. 2668C). H NMR: d 1.18(t, 3J
7.0 Hz, 6H), 3.40 (q, 3J 7.0 Hz, 4H), 6.61 (pseudod, J 9.2 Hz, 2H), 7.51 ±
7.58(m, 12H); 13C NMR: d 12.49, 44.56, 85.07, 105.24, 111.23, 111.62,
112.89, 114.69, 114.81, 114.94, 128.88, 129.08, 130.82, 134.04, 135.20, 136.15,
149.82, 152.92.
[7] B. F. Levine, C. G. Bethea, J. Chem. Phys. 1975, 66, 2666 ± 2682.
[8] I. D. Morrison, R. G. Denning, W. M. Laidlaw, M. A. Stammers, Rev.
Sci. Instrum. 1996, 67, 1445 ± 1453.
[9] a) W. Liptay, Angew. Chem. 1969, 81, 195 ± 206; Angew. Chem. Int. Ed.
Engl. 1969, 8, 177 ± 188; b) R. Wortmann, K. Elich, S. Lebus, W.
Liptay, P. Borowicz, A. Grabowska, J. Phys. Chem. 1992, 96, 9724 ±
9730. With this method the change of the molar decadic absorption
coefficient for two polarization positions and for several wavenumbers
in the region of the absorption is measured.
[10] a) J.-L. Oudar, D. S. Chemla, J. Chem. Phys. 1977, 66, 2664 ± 2668;
b) J.-L. Oudar, J. Chem. Phys. 1977, 67, 446 ± 457; c) R. Wortmann, P.
Krämer, C. Glania, S. Lebus, N. Detzer, Chem. Phys. 1993, 173, 99 ±
108; d) J. J. Wolff, D. Längle, D. Hillenbrand, R. Wortmann, R.
Matschiner, C. Glania, P. Krämer, Adv. Mater. 1997, 9, 138± 143.
[11] The intensity of the frequency doubling of w (used to determine b)
also depends on the position of the UV/Vis absorption of the
investigated molecule [Eq. (1)]. For a two-level model with ground
state g and excited state a, the frequency-independent (w !0) value
bzzz(0) is obtained from Equation (2).
1,3,5-Tricyano-2,4,6-tris(4-N,N-diethylaminophenyl)benzene (7):
A sus-
pension of 10 (256 mg, 1.00 mmol), [Pd(PPh3)4] (162 mg, 0.140 mmol),
and CuO (254 mg, 3.20 mmol) in DMF (15 mL) was heated for 10 min to
808C and then cooled to room temperature. 4-N,N-Diethylaminophenyl-
tributyltin[19] (1403 mg, 3.200 mmol) in DMF (8mL) was added, and the
mixture heated again to 858C for 8h. After cooling, the mixture was diluted
with CH2Cl2 (100 mL). It was extracted with a 10% solution of KF (3 Â )
and water (5 Â ) and then dried (MgSO4). Chromatography (silica gel,
CH2Cl2) gave a yellow product (395 mg), which was dissolved in CH2Cl2/
light petroleum (1/4). The solution was filtered and concentrated to provide
yellow needles (295 mg, 0.496 mmol, 50%), m.p. 280 ± 2848C. 1H NMR:
d 1.20 (t, 3J 7.1 Hz, 18H), 3.40 (q, 3J 7.1 Hz, 12H), 6.74 (pseudod, J
9.0 Hz, 6H), 7.47 (pseudod, J 9.0 Hz, 6H); 13C NMR: d 12.57, 44.25,
110.84, 111.99, 116.71, 120.41, 130.98, 149.32, 154.34.
1,3,5-Tricyano-2,4,6-tris(4-N,N-diethylaminophenylethynyl)benzene (8): A
solution of 10 (256 mg, 1.00 mmol), 4-N,N-diethylaminophenylacetylene
(693 mg, 4.00 mmol), [Pd(PPh3)4] (116 mg, 0.100 mmol), and CuI[18] (19 mg,
0.10 mmol) in NEt3 (3 mL) was heated to 858C for 6 h. Formation of red
crystals began after about 30 min, and a viscous, deep red suspension was
formed. Chromatography on neutral alumina (activity II; CH2Cl2/light
petroleum 1/1) yielded 8 (535 mg, 0.802 mmol, 80%); red prisms from
heptane/toluene (375 mg, 0.562 mmol, 56%), m.p. > 2308C (decomp).
1H NMR (CD2Cl2): d 1.20 (t, 3J 7.2 Hz, 18H), 3.43 (q, 3J 7.2 Hz,
12H), 6.67 (pseudod, J 8.9 Hz, 6H), 7.54 (pseudod, J 8.9 Hz, 6H);
13C NMR (CD2Cl2): d 12.66, 44.94, 84.39, 105.56, 111.01, 111.68, 112.73,
115.64, 135.11, 150.18. One signal expected on the basis of the structure
could not be detected.
w4ag
ꢀag
ꢀag
b
(À2w;w,w) b (0)
(1)
(2)
zzz
zzz
ꢀwa2g À w2ꢀw2ag À 4w2
2
6Dmazgꢀmazg
ꢀag
b
(0) lim (À2w;w,w)
zzz
2
w!0
ꢀꢀhwag
[12] A. Willets, J. E. Rice, D. M. Burland, D. P. Shelton, J. Chem. Phys.
1992, 97, 7590 ± 7599.
Received: October 6, 1999 [Z14114]
[13] K. Wallenfels, F. Witzler, K. Friedrich, Tetrahedron 1967, 23, 1845 ±
1855; the last two steps were combined to a single-step procedure in
analogy to: G. A. Olah, T. Keumi, Synthesis 1979, 112 ± 113.
[14] In analogy to a modified Stille reaction: S. Gronowitz, P. Björk, J.
Malm, A.-B. Hörnfeldt, J. Organomet. Chem. 1993, 460, 127 ± 129.
[15] In analogy to the reaction with phenyltri-tert-butyltin: H.-J. Götze,
Chem. Ber. 1972, 105, 1775 ± 1777.
[16] A. Samtleben, Ber. Dtsch. Chem. Ges. 1898, 31, 1141 ± 1148.
[17] E. Kober, C. Grundmann, J. Am. Chem. Soc. 1959, 81, 3769 ± 3770.
[18] S. Takahashi, Y. Kuroyama, K. Sonogashira, N. Hagihara, Synthesis
1980, 627 ± 630.
[1] a) J. J. Wolff, R. Wortmann, Adv. Phys. Org. Chem. 1999, 32, 121 ± 217;
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Treptow, E. Barbu, D. Längle, G. Görlitz, Chem. Eur. J. 1997, 3, 1765 ±
1773; c) H. S. Nalwa, M. Hanack, G. Pawlowski, M. K. Engel, Chem.
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Bräuchle, K. Meerholz, Chem. Phys. 1999, 245, 73 ± 78; e) C. Andraud,
T. Zabulon, A. Collet, J. Zyss, Chem. Phys. 1999, 245, 243 ± 261; f) C.
Lambert, E. Schmälzlin, K. Meerholz, C. Bräuchle, Chem. Eur. J.
1998, 4, 512 ± 521; g) C. Lambert, G. Nöll, E. Schmälzlin, K. Meerholz,
C. Bräuchle, Chem. Eur. J. 1998, 4, 2129 ± 2135; h) Y.-K. Lee, S.-J.
Jeon, M. Cho, J. Am. Chem. Soc. 1998, 120, 10921 ± 10927.
[19] In analogy to the reaction with dimethylaminophenyltributyltin: V.
Farina, B. Krishnan, D. R. Marshall, G. P. Roth, J. Org. Chem. 1993,
58, 5434 ± 5444.
[2] a) M. Joffre, D. Yaron, R. J. Silbey, J. Zyss, J. Chem. Phys. 1992, 97,
5607 ± 5615; b) J. Zyss, I. Ledoux, Chem. Rev. 1994, 94, 77 ± 105.
[3] a) I. Ledoux, J. Zyss, J. Siegel, J. Brienne, J.-M. Lehn, Chem. Phys.
Lett. 1990, 172, 440 ± 444; b) I. G. Voigt-Martin, G. Li, A. Yakimanski,
G. Schulz, J. J. Wolff, J. Am. Chem. Soc. 1996, 118, 12830 ± 12381.
[4] P. Kaatz, D. P. Shelton, J. Chem. Phys. 1996, 105, 3918± 3929.
[5] a) S. Stadler, F. Feiner, C. Bräuchle, S. Brandl, R. Gompper, Chem.
Phys. Lett. 1995, 245, 292 ± 296; b) S. Stadler, C. Bräuchle, S. Brandl,
R. Gompper, Chem. Mater. 1996, 8, 414 ± 417; c) C. Lambert, W.
Gaschler, E. Schmälzlin, K. Meerholz, C. Bräuchle, J. Chem. Soc.
Perkin Trans. 2 1999, 577 ± 587. The best 2D derivative obtained so far
was a tris(tricyanovinyl)-substituted triphenylamine described in this
paper. However, due to the strong steric hindrance in triphenylamines,
the nondipolar 2D derivative only shows a relative activity of around
0.6 with respect to the 1D analogue, which comes relatively close to
the theoretical value of 0.75 for the addition of three independent
components.
Angew. Chem. Int. Ed. 2000, 39, No. 8
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