S. Kçrsten and G. J. Mohr
m/z: 665.1 [M+], 635.2 [M+ÀNO], 605 [M+À2NO], 539.4 [M+ÀI], 509.3
[M+ÀIÀNO], 479.3 [M+ÀIÀ2NO].
Experimental Section
Tripod-4: 1H NMR (250 MHz, CDCl3, 258C, TMS): d=7.15 (d, 3J-
Reagents: Chemicals were purchased from Fluka and Aldrich and were
used without any further purification. All solvents and amines used were
of analytical reagent grade.
(H,H)=8.5 Hz, 6H), 7.48 (d, 3J(H,H)=8.5 Hz, 6H), 7.07 (d, 3J
AHCTUNGTREUNNGN ACHTUNGTRENNUNG ACHTUNGTRENNUNG
16.26 Hz, 3H), 7.25 (d, 3J
(H,H)=16.26 Hz, 3H), 7.62 (d, 3J
ACHUTGTNRENNUG ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
8.75 Hz, 6H), 8.22 ppm (d, 3J
Apparatus: The absorbance spectra of dissolved dyes were recorded on a
Perkin–Elmer Lambda 16 spectrometer. Absorption measurements were
performed by using quartz cuvettes with the respective dye solution.
Fluorescence measurements were performed on a Fluorolog 3 spectrome-
ter from Jobin Yvon-Spex. NMR spectra were recorded on Bruker AC-
250 or DRX-400 apparatus. The quantum yields were determined on a
LS50B from Perkin–Elmer by using quinine sulfate in a 0.1n H2SO4 solu-
tion. Mass spectra were obtained on a MAT SSQ 710 and on MAZ95XL
from Finnigan.
CDCl3, 258C, TMS): 124.2 (CCNO2), 124.4 (NCC), 125.2 (C=C), 126.6
(CCCNO2), 128.2 (NCCC), 131.5 (NCCCC), 132.4 (C=C), 143.9 (CNO2),
146.6 (C=CC), 147.3 ppm (NC); MS (DEI): m/z: 686 [M+], 656 [M+
ÀNO]; elemental analysis calcd (%) for C42H30N4O6: C 73.46, H 4.40, N
8.16; found: C 73.78, H 4.24, N 7.80.
Synthesis of Tripod-2: Compound 2 (0.11 g, 0.17 mmol), 2,2,2-trifluoro-1-
(4-vinylphenyl)ethanone (0.2 g, 1.0 mmol), THF (7 mL), triethylamine
(7 mL), and [PdCl2ACHTNUTRGENUG(N PPh3)2] (0.01 g) were reacted as described above for
48 h at 808C. After extraction with dichloromethane and evaporation of
the solvent, the resulting crude product was purified by column chroma-
tography with increasing solvent polarity by using a hexane/dichlorome-
thane mixture (from 5:1 to 2:1) to give Tripod-2 (30 mg, 0.04 mmol, 22%
Synthesis
Synthesis of tris(4-iodophenyl)amine (1): Triphenylamine (0.5 g,
2.04 mmol), HgO (2.06 g, 9.52 mmol), and iodine (2.59 g, 10.2 mmol)
were dissolved in ethanol (30 mL) and stirred overnight at room temper-
ature. Afterwards, the solvent was removed in vacuum. The solid residue
was redissolved in toluene (30 mL) and refluxed. The solution was fil-
tered through a short column of Al2O3 and the final product was precipi-
tated with methanol. Yield: 1.04 g (1.67 mmol, 82%); 1H NMR
yield). 1H NMR (250 MHz, CDCl3, 258C, TMS): d=7.08 (d, 3J
ACHTUNGTRENNUNG
16.4 Hz, 3H), 7.15 (d, 3J
4H), 7.25 (d, 3J
(H,H)=8.63 Hz, 2H), 7.16 (d, 3J
ACHUTGTNRENNUG CAHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
8.6 Hz, 2H), 7.66 (d, 3J
ACTHNUGRTENUNG(H,H)=8.6 Hz, 4H), 8.08 (m, 4H), 8.23 ppm (m,
2H); MS (DEI): m/z: 788 [M+], 757 [M+ÀNO].
Synthesis of Tripod-3: Compound 3 (0.1 g, 0.15 mmol), 2,2,2-trifluoro-1-
(250 MHz, CDCl3, 258C, TMS): d=7.53 (d, 3J
6.80 ppm (d, 3J(H,H)=8.4 Hz, 6H); 13C NMR (62.9 MHz, CDCl3, 258C,
(H,H)=8.7 Hz, 6H),
(4-vinylphenyl)ethanone (0.12 g, 0.6 mmol), THF (6 mL), triethylamine
ACHTUNGTRENNUNG
(5 mL), and [PdCl2ACHTNUTRGENUG(N PPh3)2] (0.05 g) were reacted as described above for
TMS): d=86.57 (CI), 126.0 (NCC), 138.45 (ICC), 146.57 ppm (NC); MS
(DEI): m/z: 622.8 [M+]; elemental analysis calcd (%) for C18H12I3N: C
34.70, H 1.94, N 2.25, I 61.11; found: C 34.99, H 1.80, N 2.20, I 61.08.
24 h at 658C. After extraction with dichloromethane and evaporation of
the solvent, the resulting crude product was purified by column chroma-
tography with increasing solvent polarity by using a hexane/dichlorome-
thane mixture (from 5:1 to 2:1) to give Tripod-3 (40 mg, 0.05 mmol, 36%
Synthesis of Tripod-1: Tris(4-iodophenyl)amine (1) (0.5 g, 0.8 mmol),
2,2,2-trifluoro-1-(4-vinylphenyl)ethanone (0.67 g, 3.3 mmol), dry THF
(5 mL), triethylamine (5 mL), and [PdCl2ACHTNUTRGNE(UNG PPh3)2] (35 mg, 0.057 mmol)
yield). 1H NMR (250 MHz, CDCl3, 258C, TMS): d=7.07 (d, 3J
ACHTUNGTRENNUNG
16.26 Hz, 3H), 7.16 (d, 3J
16.30 Hz, 2H), 7.28 (d, 3J(H,H)=16.28 Hz, 1H), 7.49 (d, 3J
8.6 Hz, 6H), 7.62 (d, 3J(H,H)=8.85 Hz, 4H), 7.65 (d, 3J
2H), 8.07 (d, 3J(H,H)=7.8 Hz, 2H), 8.22 ppm (d, 3J
(H,H)=8.6 Hz, 6H), 7.25 (d, 3J
ACHUTGTNRENNUG ACHTUNGTRENNUNG
were added to a heavy-walled reaction chamber and tightly closed. The
mixture was heated up to 1158C for 55 h. After cooling, water was added
and the reaction mixture was extracted three times with dichlorome-
thane. The combined organic phase was dried over magnesium sulfate,
filtered, and evaporated to dryness. The resulting crude product was puri-
fied by column chromatography (hexane/dichloromethane 3:1) to give
(160 mg, 0.18 mmol, 12%) Tripod-1. 1H NMR (250 MHz, CDCl3, 258C,
TMS): d=7.07 (d, 3H), 7.16 (d, 6H), 7.28 (d, 3H), 7.50 (d, 6H), 7.65 (d,
6H), 8.07 ppm (d, 6H); MS (DEI): m/z: 838 [M+ÀH]; elemental analysis
calcd (%) for C48H30F9NO3: C 68.65, H 3.60, N 1.67; found: C 68.85, H
3.55, N 1.51.
G
ACHTUNGTRENNUNG
E
ACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
4H); MS (DEI): m/z: 737 [M+], 707 [M+ÀNO]; elemental analysis calcd
(%) for C44H30F3N3O5: C 71.64, H 4.10, N 5.70; found: C 71.32, H 4.26, N
5.41.
Acknowledgements
Synthesis of compound 2, compound 3, and Tripod-4: Compound 1
This work was supported by the project MO 1062/3-1, MO 1062/5-1, and
MO 1062/6-1 of the Deutsche Forschungsgemeinschaft, and also by the
Bayerische Staatsministerium fꢅr Wirtschaft, Infrastruktur, Verkehr und
Technologie within project AZ-Nr.: 20.10-3410-2 (Projekt Sensormateria-
lien). This support is gratefully acknowledged. We thank R. Martꢁnez-
MꢂÇez, S. C. Zimmerman, and D. Weiß for stimulating discussions. We
also thank H. Mꢅller for performing fluorescence measurements and C.
Cranfield for correcting the manuscript.
(1.04 g, 1.67 mmol), 4-nitrostyrene (0.54 g, 3.62 mmol), THF (10 mL),
triethylamine (3.5 mL), and [PdCl2ACHTNUGTRNEUNG(PPh3)2] (0.07 g, 0.1 mmol) were react-
ed as described above for 48 h at 858C. The resulting crude product was
purified by column chromatography with increasing solvent polarity by
using a hexane/ethyl acetate mixture (from 5:1 to 1:1) to give the three
products in the following yields: Compound 2 (130 mg, 0.20 mmol), com-
pound 3 (150 mg, 0.23 mmol), and Tripod-4 (200 mg, 0.29 mmol).
Compound 2: 1H NMR (250 MHz, CDCl3, 258C, TMS): d=6.85 (d, 3J-
3
G
N
(d, 3J(H,H)=16.3 Hz, 1H), 7.40 (m, 2H), 7.58 (d, 3J
ACHTUNGTRENNUNG ACHTUNGTRENNUNG
[5] K. Fuji, K. Tsubaki, K. Tanaka, N. Hayashi, T. Otsubo, T. Kinoshita,
[6] T. Carofiglio, E. Lubian, I. Menegazzo, G. Saielli, A. Varotto, J. Org.
[8] T. L. Nelson, C. OꢄSullivan, N. T. Greene, M. S. Maynor, J. J. Lav-
[9] M. S. Maynor, J. J. Lavigne, Abstr. Pap. Am. Chem. Soc. 2006, 231,
23-IEC.
4H), 7.64 (m, 2H), 8.22 ppm (m, 2H); 13C NMR (62.9 MHz, CDCl3,
258C, TMS): d=86.6 (CI), 123.7 (NCC), 124.1 (NCC), 126.0 (C=C),
126.6 (NCCC), 126.9 (CCNO2), 127.0 (C=C), 129.0 (CCCNO2), 138.2
(NCCC), 138.5 (NC), 143.9 (C=CC), 146.6 (NC), 146.8 (NCCCC),
147.3 ppm (CNO2); MS (DEI): m/z: 644 [M+], 614 [M+ÀNO], 518 [M+
ÀI].
Compound 3: 1H NMR (250 MHz, CDCl3, 258C, TMS): d=6.91 (d, 3J-
ACHTUNGTRENNUNG ACHTUNGTRENNUNG ACTUHNGTRENNUGN
(H,H)=8.7 Hz, 2H), 7.05 (d, 3J(H,H)=16.7 Hz, 2H), 7.1 (d, 3J
8.8 Hz, 4H), 7.23 (d, 3J
G
ACHTUNGTRENNUNG
4H), 7.59 (d, 3J
A
ACHTUNGTRENNUNG
3
8.22 ppm (m, J
A
TMS): d=86.95 (CI), 123.7 (NCC), 124.1 (CCNO2), 125.1 (C=C), 126.6
(CCCNO2), 128.1 (NCCC), 131.3 (NCCCC), 132.4 (C=C), 138.5 (CCI),
143.9 (CNO2), 146.6 (C=CC), 146.6 (NC), 147.3 ppm (NC); MS (DEI):
974
ꢃ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 969 – 975