The Ñuorescence spectra were obtained using an FS 3000 from
Perkin-Elmer with total spectral correction, as described pre-
viously.21 A VXR 400S (Varian) instrument operating at 400
and 100.6 MHz was used to acquire the 1H and 13C NMR
spectra, respectively. Mass spectra were recorded on an SN 1B
instrument (Varian MAT).
Fluorescence quantum yield (chloroform): U \ 100%, refer-
ence N,N@-(1-hexylheptyl)perylene-3,4: 9,10-bis(dicarboximide)
(4).21 1H NMR (CDCl ): d 0.85 (t, 24 H, 8 CH ), 1.27 (m , 64
3
3
c
H, 32 CH ), 1.94 (m , 8 H, 4 a-CH ), 2.27 (m , 8 H, 4 a-CH ),
2
c
2
c
2
5.16 (p, 4 H, 4 CH), 7.52 (d, 8 H, aromatic H), 7.67 (d, 8 H,
aromatic H), 8.30 (m , 16 H, perylene aryl H), 8.55 (m , 16 H,
c
c
perylene aryl H). 13C NMR (CDCl ): d 14.1 (8 C, CH ), 22.6
Syntheses
3 3
(
8 C, CH ), 27.1 (8 C, CH ), 29.3 (8 C, CH ), 31.8 (8 C, CH ),
2
2
2
2
Tetra(4-aminophenyl)methane. Tetra(4-nitrophenyl)methane
1.5 g, 3.0 mmol), hydrazine hydrate (1.88 g, 37.5 mmol),
32.4 (8 C, CH ), 55.0 (4 C, CH), 122.9 (perylene C), 123.3
2
(
(perylene C), 125.9, 128.1, 129.2, 131.3, 132.5, 133.4, 133.8,
Raney nickel (10 g) and tetrahydrofuran (200 ml) were
reÑuxed together for 3 h. Then, the mixture was hot Ðltered,
washed twice with hot ethanol, the products precipitated from
solution and re-crystallized twice from ethanol. Yield 520 mg
134.4, 146.6, 163.2 (16 C, C2O). MS (70 eV, ESI): m/z (%) 2629
(8), 2628 (19), 2627 (33), 2626 (49) [M ] Na]`, 2070 (100)
[M ] Na [ 1 chromophore]`. Anal. for C
H
N O
1
73 156 8 16
(2603.2): calc. C 79.81, H 6.05, N 4.31; found C 79.05, H 5.95,
N 4.23%.
(
46%) of light beige crystals, m.p. 318 ¡C (dec., ref. 11 319È
3
20 ¡C). IR (KBr): l/cm~1 3421 s, 3396 s, 3351 s, 3214 m, 3025
8
m, 1621 s, 1581 m, 1508 s, 1428 w, 1273 s, 1183 s, 1131 w, 1015
m, 942 w, 828 s, 814 s, 578 s, 514 m. 1H NMR ([D] -acetone):
6
Acknowledgements
d 4.43 (s, 8 H, NH ), 6.53 (3J \ 8.5, d, 8 H, aromatic H), 6.86
2
(
3
[
3J \ 8.5 Hz, d, 8 H, aromatic H). MS (70 eV, EI): m/z (%)
This work was supported by the Deutsche Forschungsgemein-
schaft and the Fonds der Chemischen Industrie.
81 (12) [M ] 1]`, 380 (43) [M]`, 289 (23), 288 (100) [M~
C H NH ]`, 196 (10), 195 (14) [M~ [ 2 C H NH ]`, 190
6
5).
4
2
6 4
2
(
References and notes
Tetra(4-formylaminophenyl)methane (1). Tetra(4-amino-
phenyl)methane (400 mg, 1.05 mmol) and anhydrous formic
acid (10 ml) were reÑuxed for 4 h. After cooling, the product
was precipitated from solution with diethyl ether (20 ml), col-
lected by vacuum Ðltration and re-crystallized from DMF.
Yield 170 mg (33%) of light brown crystals of 1. IR (KBr):
1
J. Deisenhofer, O. Epp, K. Miki, R. Huber and H. Michel, J. Mol.
Biol., 1984, 180, 385.
2
G. McDermott, S. M. Prince, A. A. Freer, A. M. Hawthorn-
thwaite-Lawless, M. Z. Papiz, R. J. Cogdell and N. W. Isaacs,
Nature (L ondon), 1995, 374, 517.
3
4
H. Langhals, Eur. J. Org. Chem., 2001, 2481.
l/cm~1 3436 s, 3267 s, 3190 m, 3105 m, 3053 m, 2888 w, 1677
8
s, 1604 s, 1533 s, 1513 s, 1405 m, 1319 m, 1296 m, 1256 w, 1192
m, 1018 w, 822 m, 768 m. MS (70 eV, EI): m/z (%) 492 (8)
M. N. Berberan-Santos, P. Choppinet, A. Fedorov, L. Jullien and
B. Valeur, J. Am. Chem. Soc., 2000, 122, 11876.
L. Jullien, J. Canceill, B. Valeur, E. Bardez, J.-P. Lefevre, J.-M.
Lehn, V. Marchi-Artzner and R. Pansu, J. Am. Chem. Soc., 1996,
118, 5432.
5
[
[
[
3
M]`, 465 (8), 464 (28) [M~ [ CO]`, 462 (8), 436 (12)
M~ [ 2CO]`, 408 (2) [M~ [ 3CO]`, 373 (14), 372 (56)
M~ [ C H NHCHO]`, 370 (10), 345 (26), 344 (100), 343 (6),
6
K. Rothammel, Antennenbuch, 5th. edn., Teekosmos-Verlag,
Stuttgart, 1976, ISBN 3-440-04214-6.
6
5
42 (20), 317 (10), 316 (35), 314 (5), 252 (3) [M~
7
8
Review: H. Langhals, Heterocycles, 1995, 40, 477.
[
2C H NHCHO]`, 224 (5), 196 (6), 195 (18), 180 (6), 44 (17).
6
5
J. Karolin, L. B.- A . Johansson, U. Ring and H. Langhals,
Anal. for C
H
N O É H O (510.6): calc. C 68.21, H 5.14, N
9 24 4 4
0.98; found C 68.83, H 5.27, N 10.83%.
Spectrochim. Acta, Part A, 1996, 52, 747.
S. Wang, W. J. Oldham, Jr., R. A. Hudack, Jr. and G. C. Bazan,
J. Am. Chem. Soc., 2000, 122, 5695.
2
2
1
9
Tetra-4-[N-(1-Hexylheptyl)perylene-3,4: 9,10-tetracar-
10 W. S. Oldham, Jr., R. S. Lachiotte and G. C. Bazan, J. Am. Chem.
Soc., 1998, 120, 1987.
boxylicbisimid-Nº-yl]phenylmethane (3). N-(1-hexylheptyl)-
perylene-3,4: 9,10-tetracarboxylic-3,4-anhydride-9,10carbox-
imide13 (2, 200 mg, 0.35 mmol) tetra(4-formylaminophenyl)
methane (1, 90 mg, 0.2 mmol) and imidazole (4 g) were heated
under argon (180 ¡C, 4 h) and then suspended in ethanol (50
ml), acidiÐed with 2 N HCl and stirred at room temperature (2
h). The product was collected by vacuum Ðltration, thor-
oughly washed with distilled water, dried in air (100 ¡C) and
puriÐed by two column separations (Al O ] 2% H O,
1
1
F. A. Neugebauer, H. Fischer and R. Bernhardt, Chem. Ber.,
1
976, 109, 2389.
1
2
H. Langhals, R. Kollefrath and J. Lindner, Macromol. Rep. A,
1
995, 32, 415.
13 H. Kaiser, J. Lindner and H. Langhals, Chem. Ber., 1991, 124,
529.
14
15
16
H. Langhals, S. Demmig and T. Potrawa, J. Prakt. Chem., 1991,
333, 733.
A. S. Davydov, Zh. Eksp. T eor. Fiz., 1948, 18, 210; A. S.
Davydov, Chem. Abstr., 1949, 43, 4575f.
A. S. Davydov, T heory of Molecular Excitations, transl. H.
Kasaha and M. Oppenheimer, Jr., McGraw-Hill, New York,
1962.
2
3
2
chloroformÈethanol 10 : 1 and silica gel, chloroformÈacetone
5 : 1). Yield 320 mg of 3 (35%) as a red solid, m.p. [350 ¡C.
(silica gel, chloroformÈacetone 20 : 1) \ 0.20. IR (KBr):
1
R
l
8
f
17
18
19
S. Demmig and H. Langhals, Chem. Ber., 1988, 121, 225.
H. Langhals, Spectrochim. Acta, Part A, 2000, 56, 2207.
H. Langhals and W. Jona, Angew. Chem., 1998, 110, 998; H.
Langhals and W. Jona, Angew. Chem., Int. Ed., 1998, 37, 952.
/cm~1 3436 m, 2952 m, 2926 m, 2855 m, 1712 s, 1699 s, 1659
s, 1594 s, 1579 m, 1505 m, 1457 w, 1427 m, 1406 m, 1341 s,
252 m, 1154 m, 1137 w, 1123 w, 1107 w, 1020 w, 965 w, 853
w, 811 m, 794 w, 747 m, 500 w. UV/Vis (CHCl ): j /nm
1
3
max
20 R \ J; [e (j
)
[ e (j
)
]2/; [e (j
max max exp. max max exp.
H. Langhals, J. Karolin and L. B.-A. Johansson, J. Chem. Soc.,
)
]2.
(
4
e/dm3 mol~1 cm~1) 528 (380 900), 491 (213 000), 460 (75 000),
max max calcd
2
1
34 (22 100). Fluorescence (CHCl ): j /nm 624, 576, 534.
Faraday T rans., 1998, 94, 2919.
3
max
New J. Chem., 2001, 25, 1047È1049
1049