Bichromophoric perylene derivatives: Energy transfer from non-fluorescent chromophores

Article abstract of DOI:10.1002/1521-3765(20021216)8:24<5630::AID-CHEM5630>3.0.CO;2-Z

The energy of excitation at non-fluorescent chromophores such as fluorenone and anthraquinone has been trapped by a fast energy transfer to the highly fluorescent perylene bisimides. To this end, anthraquinone, fluorenone and anthracene derivatives have been linked to the perylene bisimides by non-conjugating spacers and fluorescence quantum yield of such assemblies have been determined as a function of the wavelengths of excitation. Energy transfer in such assemblies is strongly influenced by the orientation of the two chromophores. This is of interest for the construction of fluorescence switches.

Full text of DOI:10.1002/1521-3765(20021216)8:24<5630::AID-CHEM5630>3.0.CO;2-Z

FULL PAPER
Bichromophoric Perylene Derivatives: Energy Transfer from
Non-Fluorescent Chromophores
[a]
Heinz Langhals*and Sigrid Saulich
Abstract: The energy of excitation at non-fluorescent chromophores such as
fluorenone and anthraquinone has been trapped by a fast energy transfer to the
highly fluorescent perylene bisimides. To this end, anthraquinone, fluorenone and
anthracene derivatives have been linked to the perylene bisimides by non-
conjugating spacers and fluorescence quantum yield of such assemblies have been
determined as a function of the wavelengths of excitation. Energy transfer in such
assemblies is strongly influenced by the orientation of the two chromophores. This is
of interest for the construction of fluorescence switches.
Keywords: dyes/pigments ¥ energy
transfer fluorescence light-
harvesting antennae ¥ perylenes
¥
¥
Introduction
The investigation of energy transfer processes[1] is of general
interest (see for example refs. [2 9]) because of their
importance for light-harvesting in bacteria and higher
plants.[10, 11] Usually processes are studied that proceed
between highly fluorescent energy donor and acceptor
chromophores in order to prevent any loss of energy by
fluorescence quenching; see for example ref. [12 14] On the
other hand, one may ask if it is possible to use even non-
fluorescent energy donors for light harvesting if the energy
transfer to the acceptor is fast enough to compete with
fluorescence quenching.
Figure 1. Energy transfer in bichromophoric dyes.
Fluorenone and anthraquinone were applied as energy
donors. These chromophores exhibit only a weak fluorescence
themselves.[17] Pyrene, anthracene and naphthalene deriva-
tives have been used for comparison.
One nitrogen atom of 1 was used for linking energy donors.
This is an ideal position for this purpose because there are
nodes[18] in the orbitals HOMO and LUMO; this causes an
efficient electronic decoupling of the attached chromophore
and therefore, Fˆrster-type energy transfer through space is
preferred instead of the Dexter-type energy transfer[19, 20]
through bond. A further decoupling was achieved by the
introduction of sp3 hybridized links in spacers and by
arranging the two chromophores orthogonal, respectively.
The other nitrogen atom of 1 was used for the attachment of
solutizing groups such as long-chain sec-alky groups (™swal-
low-tail groups∫);[21, 22] see for example 1a) or tert-butylphenyl
groups.[23]
Results and Discussion
We used perylene-3,4:9,10-tetracarboxylic bisimides (1)[15] as
the acceptor for the study of energy transfer according to
Figure 1 because of their high fluorescence quantum yield[16]
which guarantees the preservation of the energy of excitation.
The distances of the donor chromophores and their
orientation versus 1 were varied. Therefore, they were both
directly linked to the nitrogen atoms and by means of spacers
(see Figure 1). Perylenetetracarboxylic bisimides 1 were used
as one group of starting materials for synthesis. Their partial
[a] Prof. Dr. H. Langhals, Dr. S. Saulich
Department Chemie, Universit‰t M¸nchen
Butenandtstrasse 13, 81377 M¸nchen (Germany)
Fax : (‡49)89 2180 7540
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5630 5643
saponification[24] leads to the perylenetetracarboxylic anhy-
dride imides 2. The condensation of 2 with aromatic amines
gave the directly linked bichromophoric dyes 9 (zero spacer)
and with aliphatic amines dyes 10. The condensation of 2 with
4-amino benzylic alcohol led to the dyes 6 with a hydroxy-
benzylic anchor group and the condensation with 4,4'-amino-
hydroxybiphenyl to dyes 5 with hydroxybiphenyl anchor
groups. Finally, dye 7 with the amino anchor group was
obtained by the reaction of 2 with hydrazine;[25] see Scheme 1.
The isocyanates and the amino derivative 7 were also the
starting materials for the ureas 11. Finally, the reaction of the
amine 7 with carboxylic chlorides formed the carboxylic
amides 15.
The relative energetic positions of the HOMOs of the
perylenebisimide acceptor chromophore (1) and the donor
chromophore are of central importance for the optical
behaviour of the bichromophoric dyes. The position of the
HOMO of 1 can be estimated to be about ‡1.6 V by
cyclovoltammetry (oxidation; reduction: À0.54 V).[27] The
attachment of electron deficient chromophores with low-lying
HOMOs to 1 results in a situation according to Figure 2a
which shows that the fluorescence behaviour of the acceptor
chromophore (1) is unaffected by the attached donor
chromophore. The excitation of the donor chromophore
may cause an energy transfer so that the acceptor chromo-
phore exhibits fluorescence, compare ref. [28]. However, if an
electron rich donor chromophore with a high-lying HOMO is
attached to 1 the completely different situation of Figure 2b
will be obtained. An electronic excitation of the acceptor
chromophore or an exitation by an energy transfer causes an
unoccupied electronic position in HOMO that can be filled up
by an electron transfer from the HOMO of the attached donor
chromophore, compare ref. [29]. Thus, the completely filled
HOMO of the acceptor prevents a return of the exited
electron. As a consequence, a quenching of fluorescence
results. Such an electron transfer between the HOMOs
competes with fluorescence and the relative rates between
the two processes determine the over-all fluorescence quan-
tum yield. The rate of the electron transfer depends on the
energetic difference between the two HOMOs and Mar-
cus[30, 31] theory may be a useful approach for a quantitative
description. This concept can also explain the still unresolved
problem[32](W¸rthner and co-worker) that the fluorescence
quantum yield of a perylene bisimide with attached trialkoxy-
phenyl groups is low whereas a substitution of the perylene
nucleus with electron donor groups increases the fluorescence
quantum yield stepwise with the number of such groups; these
groups increase the HOMO of the perylene dye chromophore
so that it is pushed above the HOMO of the substituent.
The comparably electron rich napthalene, anthracene and
pyrene derived bichromophores exhibit low fluorescence
quantum yields. This corresponds to the situation of Fig-
ure 2b. On the other hand, anthraquinone and fluorenone are
sufficiently electron deficient so that the situation of Fig-
ure 2a is obtained if they are linked to the perylene bisimides;
all of these derivatives exhibit high fluorescence quantum
yields if the perylene bisimide chromophore is directly
irradiated, for example at 490 nm. This clearly indicates
additionally that the two linked chromophores are essentially
independent of each other, especially, because no interference
by the non-fluorescent attached chromophores is observed.
The additional absorption of the attached chromophores
can be calculated from the UV/Vis spectra by subtraction of
the spectrum of the basic perylene dye 1a; the orbital nodes in
HOMO and LUMO of 1 are therefore important because
they isolate the attached chromophores and render the UV/
Vis spectra of the perylene bisimide unit nearly independent
from attached groups. We concentrated on the effects of
Scheme 1. Preparation of perylene dyes with anchor groups.
The perylene anhydride imide 3 was obtained in a two-step
synthesis from the technical perylene-3,4:9,10-tetracarboxylic
bisanhydride through the easily accessible perylenentetracar-
boxylic anhydride monopotassium salt[24] and its condensation
with ammonia.[26] The bisimides 4 were obtained by a
condensation of 3 with primary amines. The hydroxyethyl
anchor group, dyes 8, was introduced by nucleophilic dis-
placement reaction with 4. Dye 4 was also the starting
material for dyes with methylene spacers because a nucleo-
philic displacement reaction with benzylic bromides proceeds
easily.
The dyes 5, 6 and 8 with a hydroxy anchor group were
linked to the second chromophore by an esterification using
the corresponding carboxylic acid chlorides so that dyes 13, 14
and 16 were obtained (see Scheme 2). The reaction of the
hydroxy derivatives with isocyanates gave the urethanes 12.
Chem. Eur. J. 2002, 8, No. 24
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H. Langhals and S. Saulich
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Scheme 2. Bichromophoric perylene dyes.
anthraquinone as a donor chro-
mophore because the absorp-
tion of the fluorenone is mainly
below 300 nm and thus causes
more experimental difficulties.
The additional absorption by
the anthraquinone chromo-
phore lies between 300 and
350 nm and it is in this spectral
region about twice as high as
the absorption of the perylene
bisimide.
A plot of the fluorescence
quantum yield as a function of
the wavelengths of excitation is
a useful indicator of the effi-
ciency of energy transfer be-
tween the two chromophores.
One finds high fluorescence
quantum yields, nearly unity,
for the majority of anthraqui-
none containing bichromo-
phores (9 16) if the region of
long wavelength is irradiated
(chromophore of 1) and a sharp
drop is found: for the irradia-
Figure 2. Energy and electron transfer in bichromophoric dyes as discussed in the text.
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Bichromophoric Perylene Derivatives
5630 5643
tion at about 350 nm; see for example 16a in Figure 3 and 10a
where the spacer is longer and more flexible in Figure 4 (a
rather high level of noise is obtained at about 400 nm because
of the low absorptivity of the dye in this spectral region) or in
9b with a zero spacer; see Figure 5. The constantly high
fluorescence quantum yield in the region of long wavelengths
is an additional indicator for the independency of the two
chromophores. A further proof of this independence is given
by the measurements of fluorescence lifetimes;[33] these are
independent of the attached chromophore and identical with
the monochromophoric dye 1a; see Table 1. The conclusion is
that the influence of the second chromophore on the
electronic transitions of the perylene bisimide units (1) is
negligible.
Table 1. Fluorescence lifetimes of perylene dyes in chloroform.
t[c] [ns]
[a]
[b]
Dye
lexc [nm]
lem [nm]
1a
261
300
497
261
300
497
261
300
497
> 520
> 500
> 550
> 520
> 500
> 550
> 520
> 500
> 550
3.792
3.958
3.937
3.858
3.911
3.901
3.933
3.911
3.930
16b
16 f
[a] Wavelengths of excitation. [b] Spectral region of emission. [c] Time
constant for fluorescence decay (monoexponential).
The sharp drop of fluorescence quantum yield matches the
additional absorption of the attached anthraquinone. There-
fore, energy transfer cannot compete with fluorescence
deactivation for the majority of anthraquinone derivatives
and this is not dependent on whether the anthraquinone is
directly connected to the imide nitrogen atom of 1 (dyes 9) or
by different spacers (dyes 10 16); see for example 9b in
Figure 4. On the other hand, these drops proceed not to zero,
but to fluorescence quantum yields of about 40%; this
corresponds to the ratio of absorptivities between the linked
anthraquinone and the perylenbisimide chromophore at these
wavelengths. The conclusion is that the excitation of the two
chromophores results in two individual and independent
pathways for the fate of the energy of excitation; the energy
transmitted to the anthraquinone unit will be lost, however, if
energy is transferred to the perylene bisimide it cannot come
to the anthraquinone chromophore and will be emitted as
fluorescent light. This is remarkable because two energetically
similar levels might result in mixing; see the absorption of 12a
in Figure 6 in which the attached chromophore shows an
absorption over a broad spectral region.
Figure 3. UV/Vis absorption spectra (E) of dye 16a (thick line) compared
with 1a (thin line) in chloroform and fluorescence quantum yield (F) of
16a as a function of the wavelength of excitation (upper noisy line);
emission at 577 nm.
Figure 4. UV/Vis absorption spectra (E) of dye 10a (thick line) compared
with 1a (thin line) in chloroform and fluorescence quantum yield (F) of
10a as a function of the wavelength of excitation (upper noisy line);
emission at 577 nm.
Figure 5. UV/Vis absorption spectra (E) of dye 9b (thick line) compared
with 1a (thin line) in chloroform and fluorescence quantum yield (F) of 9b
as a function of the wavelength of excitation (upper noisy line); emission at
577 nm.
Figure 6. UV/Vis absorption spectra (E) of dye 12a (thick line) compared
with 1a (thin line) in chloroform and fluorescence quantum yield (F) of
12a as a function of the wavelength of excitation (upper noisy line);
emission at 577 nm.
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H. Langhals and S. Saulich
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The anthraquinone derivative 9a is an exception to this
behaviour because an unaltered high fluorescence quantum
yield is observed even for an excitation between 300 and
350 nm where the anthraquinone unit absorbs light; see
Figure 7. The conclusion is that in 9a a very efficient energy
transfer proceeds from the anthraquinone chromophore to
the perylene bisimide chromophore. This is remarkable
because no such energy transfer proceeds in the position
isomeric dyes 9b. This is certainly a consequence of the
special and rigid orientation of the two chromophores.
Therefore, the orientation of two chromophores is of special
importance for the efficiency of energy transfer, especially for
transfer from chromophores with low fluorescence quantum
yields.
where there are maxima in the absorption of the anthracene
unit; see Figure 8. This indicates that there is not only a
fluorescence quenching by the attached anthracene unit, but
also an independent way for energy loss if the anthracene unit
is optically excited; this is in as far remarkable as many
9-anthracenyl derivatives exhibit strong fluorescence. A
possible explanation for the unusual behaviour of the
anthracenyl derivative is given by the fact that it is appreciably
less photostable than the other perylene derivatives. Many
reaction products are found after irradiation for several days
with sunlight. These products could not be separated; how-
ever, the UV/Vis spectrum of the mixture clearly indicates
that the perylenen bisimide chromophore persists, whereas
the anthracene unit is destroyed.
Figure 8. UV/Vis absorption spectra (E) of dye 10c (thick line) compared
with 1a (thin line) in chloroform and fluorescence quantum yield (F) of
10c as a function of the wavelength of excitation (upper noisy line);
emission at 577 nm.
Figure 7. UV/Vis absorption spectra (E) of dye 9a (thick line) compared
with 1a (thin line) in chloroform and fluorescence quantum yield (F) of 9a
as a function of the wavelength of excitation (upper noisy line); emission at
577 nm.
Similar effects concerning energy transfer seem to be
important for the naphthalene, anthracene and pyrene
derivatives. The additional absorption of the second chromo-
phore is more pronounced than for the anthraquinone
derivatives, however, the energy transfer processes cannot
be as unequivocally determined as for the anthraquinone
derivatives because of their lower fluorescence quantum
yields. Special effects seem to be important for the anthracene
derivatives 10. There is not only a diminishing of the
fluorescence quantum yield in 10c to less than 40%, but
there is a further drop below 400 nm where the anthracene
unit absorbs light and minima in fluorescence quantum yield
Conclusion
Chromophores with low fluorescence quantum yields can be
used as light-harvesting systems if their energy of excitation is
fast enough transferred to a highly fluorescent acceptor. Not
only the distance of the donor to the acceptor needs to be
therefore controlled, but also the relative positions of the
HOMO of the two chromophores and the orientation of the
chromophores versus each other. The control of the energy
transfer by the relative orientation of the chromophores is
also important for the construction of energy transfer
switches, see Figure 9; for fluorescence quenching switches
Figure 9. Switch for energy transfer by the orientation of chromophores.
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Bichromophoric Perylene Derivatives
5630 5643
3J(H,H) ˆ 8.0 Hz, 2H; 2CH perylene), 8.58 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH
perylene), 8.62 (d, 3J(H,H) ˆ 7.9 Hz, 4H; 4CH perylene), 8.72 (s, 1H; NH).
compare[34, 35] and molecular switches compare ref. [36]. Such
a control can be used for optical computing[37, 38] in which the
transport of electrical energy by wires in conventional
computing is replaced by the oriented transfer of optical
energy; for molecular data processing compare ref. [39].
Arrangements of chromophores with switchable energy
transfer may be also important for FRET-systems (™Fluo-
rescence Resonance Energy Transfer∫) in biochemistry for
the analysis of DNA.
Preparation of N-alkyl-N'-hydroxyethyl-perylene-3,4:9,10-tetracarboxylic
bisimides (8)–General procedure: N-alkyl-perylene-3,4:9,10-tetracarbox-
ylic bisimides (4) (1.22 mmol), 2-bromoethanol (5.02 g, 40.2 mmol),
anhydrous potassium carbonate (4.67 g, 33.8 mmol) and anhydrous DMF
(40 mL) were stirred at 1008C for 24 h, added to water, acidified with 1n
HCl, collected by vacuum filtration, washed three times with distilled
water, dried under air, and purified by column separation (silica gel,
chloroform/acetone 15:1, broad red band).
N-(1-Hexylheptyl)-N'-(2-hydroxyethyl)-perylene-3,4:9,10-tetracarboxylic
diimide (8a): N-(1-Hexylheptyl)-perylene-3,4:9,10-tetracarboxylic diimide
(4a) (700 mg, 1.22 mmol) was allowed to react according to the general
procedure to yield the title compound a red dye (510 mg, 68%). M.p.
>3008C; Rf (silica gel, CHCl3/acetone 15:1) ˆ 0.31; IR (KBr) nÄ ˆ3441 brm
(OH), 2955s, 2928s, 2857s, 1697s, 1658s, 1595s, 1579m, 1439w, 1405m,
1342s, 1251w, 1173w, 1055w, 852w, 810s, 746 cmÀ1 s; 1H NMR (400 MHz,
CDCl3, 258C, TMS): d ˆ 0.83 (t, 6H; 2CH3), 1.24 (m, 16H; 8CH2), 1.88 (m,
Experimental Section
Spectra: UV/Vis absorption spectra: OMEGA 20 from Bruins. Fluores-
cence spectra and fluorescence quantum yields: Fluorescence Spectrom-
eter 3000 totally corrected according to ref. [28]; the fluorescence quantum
yields were obtained by the integration of the emission from 500 800 nm.
Fluorescence excitation spectra: LS50B from Perking Elmer, totally
corrected according to ref. [28]; the emission at 490 nm has been used as
the reference for fluorescence quantum yields from the integration for the
measurements for the wavelengths dependence of fluorescence quantum
yields.
3
2H; a-CH2), 2.25 (m, 2H; a-CH2), 4.81 (t, J(H,H) ˆ 5.2 Hz, 2H; 1CH2),
4.04 (brs, 2H; 1CH2), 4.50 (t, 2H; 1CH2), 5.18 (m, 1H; 1CH), 8.56 (d,
3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.58 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH
perylene), 8.66 (d, 3J(H,H) ˆ 7.9 Hz, 4H; 4CH perylene); 13C NMR
(CDCl3): d ˆ 14.05 (2C, CH3), 22.60, 26.93, 29.24, 31.78, 32.41 (10C,
CH2), 42.97 (1C, CH2-NR2), 54.88 (1C, CH), 61.73 (1C, CH2-OH), 122.87,
122.96, 123.27, 126.48, 126.51, 129.51, 131.25, 134.18, 135.04 (20C, CH
Extractive recrystallization: The recrystallization of dyes was combined
with an extraction according to ref. [40].
ˆ
perylene), 164.24 (4C, C O); UV/Vis (CHCl3): lmax (e) ˆ 261 (31510), 370
(4120), 435 (4660), 460 (17040), 491 (47980), 528 nm (80200); fluorescence
Preparation of N-alkyl-perylene-3,4:9,10-tetracarboxylic bisimides (4)–
General procedure: Perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-
imide (2.0 g, 5.1 mmol), the corresponding alkylamine (8.13 mmol) and
imidazole (15 g) were stirred under argon (1608C, 2 h), having cooled to
room temperature and stirred with a mixture of ethanol/2n HCl (100 mL,
30 min). The precipitate was collected by vacuum filtration, treated twice
with boiling aqueous potassium carbonate solution (100 mL, 10%, 30 min),
washed thoroughly with distilled water, dried under air (1208C, 16 h), and
purified by column separation (silica gel 52X 4 cm) where an orange
forerun was removed with chloroform and the main fraction was obtained
with chloroform/acetic acid 10:1 as a broad orange red band.
(CHCl3): lmax (Irel) ˆ 542 (1), 576 nm (0.54); MS (70 eV): m/z (%): 617 (13)
‡
‡
‡
[M ‡H], 616 (30) [M ], 599 (7), 447 (6), 436 (17), 435 (51) [M À C13H26],
‡
434 (42) [M À C13H26 À H], 417 (8), 404 (11), 403 (7), 393 (6), 392 (33), 391
‡
‡
(100), 390 (47) [M À C13H26 À C2H3OH], 373 (17), 347 (6), 346 (13) [M
À
C13H26 À CH3OH À CO2], 345 (18); elemental analysis calcd (%) for
C44H42N2O5 (616.8): C 75.95, H 6.54, N 4.54; found: C 75.71, H 6.77, N 4.51.
N-(1-Heptyloctyl)-N'-(2-hydroxyethyl)-perylene-3,4:9,10-tetracarboxylic
diimide (8b): N-(1-Heptyl-octyl)-perylene-3,4:9,10-tetracarboxylic diimide
(4b, 730 mg, 1.22 mmol) was allowed to react according to the general
procedure. Yield 490 mg (62%), m.p. > 3008C; Rf (silica gel, CHCl3/
acetone 15:1) ˆ 0.27; IR (KBr): nÄ ˆ3439brm (OH), 2926s, 2855s, 1694s,
1658s, 1595s, 1439w, 1404m, 1342s, 1251w, 1173w, 810s, 746 cmÀ1 s;
1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.83 (t, 6H; 2CH3), 1.28 (m,
20H; 10CH2), 1.89 (m, 2H; a-CH2), 2.25 (m, 2H; a-CH2), 2.44 (brs, 1H;
OH), 4.04 (brs, 2H; 1CH2), 4.48 (t, 3J(H,H) ˆ 5.2 Hz, 2H; 1CH2), 5.17 (m,
1H; 1CH), 8.44 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.47 (d,
3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.57 (d, 3J(H,H) ˆ 7.9 Hz, 4H;
4CH perylene); 13C NMR (CDCl3): d ˆ 14.05 (2C, CH3), 22.61, 27.03, 29.23,
29.52, 31.80, 32.37 (12C, CH2), 42.95 (1C, CH2-NR2), 54.90 (1C, CH), 61.60
(1C, CH2-OH), 122.76, 122.83, 123.13, 126.13, 126.26, 129.32, 129.38, 131.51,
N-(1-Hexylheptyl)-perylene-3,4:9,10-tetracarboxylic diimide (4a): Pery-
lene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carboximide
(2.0 g,
5.1 mmol) and 7-aminotridecane (1.62 g, 8.13 mmol) were allowed to react
and purified according to the general procedure (2.16 g, 74%). M.p.
>3008C; Rf (silica gel/CHCl3/HOAc 10:1) ˆ 0.85; IR (KBr): nÄ ˆ 3065w,
2956m, 2926m, 2856m, 1696s, 1660s, 1594s, 1437m, 1403m, 1374w, 1344s,
1273m, 1247w, 1176w, 811w, 743w, 655 cmÀ1 m; 1H NMR (400 MHz,
CDCl3, 258C, TMS): d ˆ 0.83 (t, 6H; 2CH3), 1.24 (m, 10H; 5CH2), 1.33 (m,
6H; 3CH2), 1.87 (m, 2H; a-CH2), 2.25 (m, 2H; a-CH2), 5.19 (m, 1H; 1CH),
8.60 (d, 3J(H,H) ˆ 8.0 Hz, 2H; 2CH perylene), 8.62 (d, 3J(H,H) ˆ 8.1 Hz,
2H; 2CH perylene), 8.66 (d, 3J(H,H) ˆ 7.9 Hz, 4H; 4CH perylene), 8.83
(brs, 1H; 1NH).
ˆ
133.97, 134.81 (20C, CH perylene), 164.09 (4C, C O); MS (70 eV): m/z
‡
‡
(%): 645 (13) [M ‡H], 644 (29) [M ], 527 (8), 436 (18), 435 (51), 434 (46),
‡
417 (6), 404 (6), 403 (5), 393 (5), 392 (30), 391 (100), 390 (40) [M
C15H30 À C2H3OH], 373 (12), 346 (9) [M À C15H30 À C2H3OH À CO2], 345
À
‡
N-(1-Heptyloctyl)-perylene-3,4:9,10-tetracarboxylic diimide (4b): Pery-
(11).
lene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carboximide
(2.0 g,
5.1 mmol) and 8-aminopentadecane (1.85 g, 8.13 mmol) were allowed to
react and purified according to the general procedure (2.36 g, 77%). M.p.
>3008C; Rf (silica gel/CHCl3/HOAc 10:1) ˆ 0.87; IR (KBr): nÄ ˆ3179w br.
(NH), 3068w, 2956m, 2926m, 2855m, 1697s, 1658s, 1554s, 1579m, 1435w,
1403m, 1354m, 1344s, 1273m, 1245w, 1177w, 810m, 742w, 655 cmÀ1 m;
1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.82 (t, 6H; 2CH3), 1.29 (m,
20H; 10CH2), 1.87 (m, 2H; a-CH2), 2.26 (m, 2H; a-CH2), 5.18 (m, 1H;
1CH), 8.58 (brs, 1H; NH), 8.62 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene),
8.62 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.66 (d, 3J(H,H) ˆ 8.0 Hz,
4H; 4CH perylene).
N-(1-Nonyldecyl)-N'-(2-hydroxyethyl)-perylene-3,4:9,10-tetracarboxylic
bisimide (8c): N-(1-Nonyldecyl)-perylene-3,4:9,10-tetracarboxylic bis-
imide (4c, 800 mg, 1.22 mmol) was allowed to react according to the
general procedure (600 mg, 70%). M.p. >3008C; Rf (silica gel, CHCl3/
acetone 15:1) ˆ 0.20; IR (KBr): nÄ ˆ3450 brm (OH), 2925s, 2854s, 1697s,
1653s, 1595s, 1579m, 1457w, 1405m, 1343s, 1254w, 1171w, 1061w, 810s,
746 cmÀ1 s; 1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.81 (t, 6H;
2CH3), 1.23 (m, 28H; 14CH2), 1.87 (m, 2H; a-CH2), 2.24 (m, 2H; a-CH2),
2.38 (brs, 1H; OH), 4.02 (t, 3J(H,H) ˆ 5.0 Hz, 2H; 1CH2), 4.47 (t,
3J(H,H) ˆ 4.9 Hz, 2H; 1CH2), 5.15 (m, 1H; 1CH), 8.45 (d, 3J(H,H) ˆ
8.0 Hz, 2H; 2CH perylene), 8.48 (d, 3J(H,H) ˆ 8.0 Hz, 2H; 2CH perylene),
8.57 (d, 3J(H,H) ˆ 8.0 Hz, 4H; 4CH perylene); 13C NMR (CDCl3): d ˆ
14.08 (2C, CH3), 22.64, 27.01, 29.27, 29.55, 31.86, 32.36 (16C, CH2), 43.23
(1C, CH2-NR2), 54.88 (1C, CH), 61.63 (1C, CH2-OH), 122.77, 122.85,
123.16, 126.48, 126.51, 129.35, 131.54, 134.01, 134.85 (20C, CH Perylen),
N-(1-Nonyldecyl)-perylene-3,4:9,10-tetracarboxylic diimide (4c): Pery-
lene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carboximide
(2.0 g,
5.1 mmol) and 10-aminononadecane (2.30 g, 8.13 mmol) were allowed to
react and purified according to the general procedure (1.74 g, 51%). M.p.
>3008C; Rf (silica gel/CHCl3/HOAc 10:1) ˆ 0.87; IR (KBr): nÄ ˆ 3179w br.
(NH), 3068w, 2956m, 2925s, 2854s, 1697s, 1660s, 1554s, 1465w, 1457w,
1403m, 1354m, 1344s, 1273m, 811s, 655 cmÀ1 m; 1H NMR (400 MHz,
CDCl3, 258C, TMS): d ˆ 0.82 (t, 6H; 2CH3), 1.27 (m, 28H; 14CH2), 1.88
(m, 2H; a-CH2), 2.26 (m, 2H; a-CH2), 5.18 (m, 1H; 1CH), 8.56 (d,
ˆ
164.13 (4C, C O); UV (CHCl3): lmax(e) ˆ 261 (28470), 370 (2170), 433 sh
(3340), 460 (15720), 491 (45970), 528 nm (77640); fluorescence (CHCl3):
lmax (Irel) ˆ 536 (1.00), 579 (0.53), 626 nm (0.12); fluorescence quantum
yield (lexc ˆ 490 nm, E490 nm ˆ 0.0251/1 cm, CHCl3, reference 1a with
Chem. Eur. J. 2002, 8, No. 24
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0947-6539/02/0824-5635 $ 20.00+.50/0
5635

H. Langhals and S. Saulich
FULL PAPER
‡
‡
F ˆ 1.00) ˆ 0.97; MS (70 eV): m/z (%): 701 (23) [M ‡H], 700 (43) [M ],
54.82 (1C, CH), 115.71, 123.08, 123.25, 123.33, 126.51, 127.78, 128.63, 128.79,
129.60, 129.93, 131.93, 134.37, 135.25, 141.46 (32C, CH perylene, CH
‡
‡
683 (10) [M À OH], 447 (5), 436 (28), 435 (80) [M À C19H37], 434 (64)
‡
ˆ
[M À C19H37 À H], 417 (6), 404 (9), 403 (6), 393 (6), 392 (31), 391 (88), 390
biphenyl), 163.69 (4C, C O); UV (CHCl3): lmax (e) ˆ 261 (55520), 279 sh
‡
‡
(46) [M À C19H37 À C2H3OH], 373 (6), 346 (5) [M À C19H37 À C2H3OH À
CO2], 345 (6); elemental analysis calcd (%) for C45H52N2O5 (700.4): C 77.11,
H 7.48, N 4.00; found: C 76.67, H 7.37, N 3.82.
(23510), 351 (4640), 369 (5190), 431 sh (6350), 459 (20480), 490 (55320),
527 nm (91630); fluorescence (CHCl3): lmax (Irel) ˆ 535 (1.00), 575 (0.55),
‡
‡
629 nm (0.14); MS (70 eV): m/z (%): 741 (13) [M ‡H], 740 (25) [M ], 560
‡
(23), 559 (75), 558 (100) [M À C13H26], 557 (10), 373 (21); elemental
N-(3,5-Di-tert-butylphenyl)-N'-(2-hydroxyethyl)-perylene-3,4:9,10-tetra-
carboxylic bisimide (8d): N-(3,5-Di-tert-butylphenyl)-perylene-3,4:9,10-
tetracarboxylic bisimide (4d, 800 mg, 1.2 mmol) was allowed to react
according to the general procedure (600 mg, 70%). M.p. >3008C; Rf (silica
gel, CHCl3/acetone 15:1) ˆ 0.20; IR (KBr): nÄ ˆ3441brm (OH), 2963m,
1700s, 1663s, 1595s, 1579m, 1506w, 1437m, 1404m, 1358s, 1345s, 1252m,
1174w, 1064w, 825w, 811m, 748m, 651 cmÀ1 m; MS (70 eV): m/z (%): 623
analysis calcd (%) for C49H44N2O5 (740.9): C 79.44, H 5.99, N 3.78; found: C
79.20, H 6.11, N 4.02.
Fluorene-9-one-1-carboxylic chloride: Fluorenone-1-carboxylic acid
(1.00 g, 4.46 mmol), thionyl chloride (5.0 mL, 69 mmol) an one drop of
pyridine were heated under reflux with the exclusion of moisture for
30 min. Subsequently, thionyl chloride was removed in vacuo, anhydrous
toluene (1 mL) was added as an entrainer and then removed in vacuo. The
residue was recrystallized from anhydrous toluene and dried over
phosphorous pentaoxide and paraffin to yield the title compound
(460 mg, 43%) as a yellow solid. IR (KBr): nÄ ˆ1775w (COCl), 1715s,
1675w, 1607s, 1468m, 1415m, 1297w, 1139m, 932m, 735s, 687 cmÀ1 w.
‡
‡
‡
(3) [M ‡H], 622 (6) [M ], 610 (2), 609 (6), 608 (2), 607 (5) [M À CH3],
‡
‡
605 (2) [M À OH], 567 (9), 566 (40), 565 (100) [M À C(CH3)3], 563 (2),
‡
551 (3), 550 (4), 549 (8), 535 (2), 522 (4), 521 (7) [M À C(CH3)3 À
C2H3OH], 505 (3).
N-(1-Hexylheptyl)-N'-(4-hydroxymethyl-phenyl)-perylene-3,4:9,10-tetra-
carboxylic bisimide (6a): N-(1-Hexylheptyl)-perylene-3,4:9,10-tetracar-
boxylic-3,4-carboximide-9,10-anhydride (2a, 1.03 g, 1.79 mmol), 4-amino-
benzylalcohol (300 mg, 2.43 mmol), zinc acetate dihydrate (100 mg,
0.46 mmol) and imidazole (10 g) were stirred at 1608C for 2 h, cooled to
room temperature, treated with a small amount of ethanol, acidified with
HCl (2n), stirred for 30 min, collected by vacuum filtration, treated two
times with boiling potassium carbonate solution (100 mL, 10%, 15 min),
collected by vacuum filtration, thoroughly washed with distilled water,
dried in air (1208C, 16 h), purified two times by column separation (silica
gel, chloroform/ethanol 20:1 and chloroform/acetone 15:1) to yield a red
powder (170 mg, 14%). M.p. >3508C; Rf (silica gel, CHCl3/acetone
15:1) ˆ 0.18; IR (KBr): nÄ ˆ3448 brm (OH), 3075w, 2954s, 2928s, 2856s,
1698s, 1658s, 1594s, 1579m, 1512w, 1458w, 1434m, 1405s, 1344s, 1255s,
1200w, 1177m, 852w, 811s, 793w, 746 cmÀ1 s; 1H NMR (400 MHz, CDCl3,
258C, TMS): d ˆ 0.81 (t, 6H; 2CH3), 1.26 (m, 16H; 8CH2), 1.86 (m, 2H; a-
CH2), 2.23 (m, 2H; a-CH2), 4.81 (s, 2H; 1CH2), 5.17 (m, 1H; 1CH), 7.34 (d,
3J(H,H) ˆ 8.2 Hz, 2H; 2CH phenyl), 7.58 (d, 3J(H,H) ˆ 8.2 Hz, 2H; 2CH
phenyl), 8.65 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.67 (d, 3J(H,H) ˆ
8.1 Hz, 2H; 2CH perylene), 8.73 (d, 3J(H,H) ˆ 8.1 Hz, 4H; 4CH perylene);
13C NMR (CDCl3): d ˆ 14.01 (2C, CH3), 22.55, 26.91, 29.18, 31.73, 32.36
(10C, CH2), 54.82 (1C, CH), 64.94 (1C, CH2-OH), 123.07, 123.25, 123.34,
124.41, 126.33, 126.75, 127.87, 128.63, 129.57, 129.89, 131.90, 133.91, 134.38,
135.23, 139.11, 141.67, 148.25 (26C, CH perylene, CH phenyl), 164.2 (4C,
Fluorene-9-one-2-carboxylic chloride: Fluorenone-2-carboxylic acid
(1.00 g, 4.46 mmol) was allowed to react according to fluorene-9-one-1-
carboxylic chloride to yield the title compound (690 mg, 64%). M.p. 174
1758C; IR (KBr): nÄ ˆ1749s (COCl), 1734s, 1717s, 1616s, 1602m, 1581w,
1427w, 1216m, 1204w, 1183s, 1105s, 979m, 882m, 848m, 774s, 768s, 741s,
667s, 647 cmÀ1 s.
Anthraquinone-2-carboxylic chloride: Anthraquinone-2-carboxylic acid
(1.00 g, 3.96 mmol) was allowed to react according to fluorene-9-one-1-
carboxylic chloride to yield the title compound (690 mg, 63%). IR (KBr): nÄ
ˆ
ˆ1743s (COCl), 1672s (C O), 1589s, 1296s, 1206s, 881m, 712m,
682 cmÀl s.
Fluore-9-one-2-isocyanate: Fluorene-9-one-2-carboxylic chloride (600 mg,
2.48 mmol) was dissolved in anhydrous toluene (20 mL). The solution was
added to a suspension of sodium azide (320 mg, 5.00 mmol) in dry toluene,
heated under reflux for 20 h, filtrated and evaporated in vacuo to yield the
title compound as a yellow solid (440 mg, 81%). IR (nujol): nÄ ˆ2279s
(NCO), 1724s, 1603s, 1587w, 1516w, 1424w, 1295m, 1287m, 1264m,
1192m, 837s, 763s, 735s, 572 cmÀ1 s.
Anthraquinone-2-isocyanate:
Anthraquinone-2-carboxylic
chloride
(610 mg, 2.5 mmol) was allowed to react according to fluore-9-one-2-
isocyanate to yield the title compound as a yellow solid (590 mg, 95%). IR
(nujol): nÄ ˆ2283brs (NCO), 1680s, 1669w, 1589m, 1577w, 1326m, 1297m,
1175w, 718w, 710 cmÀ1 m.
ˆ
C O); UV (CHCl3): lmax (e) ˆ 261 (36960), 369 (3420), 435 (3780), 459
9-Bromomethyl-anthracene:
9-Hydroxymethyl-anthracene
(500 mg,
(17290), 491 (50620), 527 nm ((85250); fluorescence (CHCl3): lmax (Irel) ˆ
2.4 mmol) was suspended in anhydrous toluene (10 mL), heated to 808C
for 2 h after having added phosphoric tribromide (0.3 mL, 3.2 mmol),
having cooled to room temperature, shaken with aqueous NaHCO3
(20 mL, 5%), dried (CaCl2) and evaporated to yield the title compound
as a (90 mg, 14%). IR (KBr): nÄ ˆ3053w, 1623m, 1449m, 1198s, 1156w,
1055w, 957w, 883m, 844w, 787m, 730s, 692w, 601w, 550m, 489 cmÀ1 w; MS
535 (1.00), 577 (0.52), 625 nm (0.12); fluorescence quantum yield (lexc
ˆ
490 nm, E490 nm ˆ 0.0311/1 cm, CHCl3, reference 1a with F ˆ 1.00) ˆ 1.01;
‡
‡
MS (70 eV): m/z (%): 679 (10) [M ‡H], 678 (21) [M ], 560 (9), 498 (23),
‡
‡
497 (70), 496 (100) [M À C13H26], 495 (19), 467 (14), 390 (18) [M
À
C13H26 À C7H5OH], 373 (20), 345 (7); elemental analysis calcd (%) for
C44H42N2O5 (678.8): C 77.85, H 6.24, N 4.13; found: C 77.60, H 6.27, N 4.16.
‡
‡
‡
(70 eV): m/z (%): 273 (1) [M ‡H], 272 (8) [M ], 271 (2) [M ‡H], 270 (8)
N-(1-Hexylheptyl)-N'-(4-(4'-hydroxybiphenyl))-perylene-3,4:9,10-tetracar-
boxylic bisimide (5a): N-(1-Hexylheptyl)-perylene-3,4:9,10-tetracarboxyl-
ic-3,4-carboximide-9,10-anhydride (2a, 300 mg, 0.52 mmol), 4-aminobi-
phenyl-4-ol (100 mg, 0.54 mmol), zinc acetate dihydrate (100 mg,
0.46 mmol) and imidazole (3.5 g) were stirred at 1408C for 2 h, cooled to
room temperature, treated with a small amount of ethanol, acidified with
HCl (2n), stirred for 30 min, collected by vacuum filtration, treated two
times with boiling potassium carbonate solution (100 mL, 10%, 15 min),
collected by vacuum filtration, thoroughly washed with distilled water,
dried in air (1208C, 16 h), purified two times by column separation (silica
gel, chloroform/ethanol 20:1 and chloroform/acetone 15:1) to yield a red
powder (240 mg, 62%). M.p. >3508C; Rf (silica gel, CHCl3/acetone
15:1) ˆ 0.45; IR (KBr): nÄ ˆ3420 (brm, OH), 3070w, 2954s, 2927s, 2856s,
1698s, 1658s, 1594s, 1579s, 1502m, 1434m, 1405m, 1343s, 1255s, 1193w,
1175m, 850m, 825m, 811s, 746 cmÀ1 s; 1H NMR (400 MHz, CDCl3, 258C,
TMS): d ˆ 0.80 (t, 6H; 2CH3), 1.24 (m 16H; 8CH2), 1.85 (m, 2H; a-CH2),
2.24 (m, 2H; a-CH2), 4.83 (s, 1H; 1 OH), 5.16 (m, 1H; 1CH), 6.90 (d,
3J(H,H) ˆ 8.6 Hz, 2H; 2CH biphenyl), 7.36 (d, 3J(H,H) ˆ 8.6 Hz, 2H; 2CH
biphenyl), 7.51 (d, 3J(H,H) ˆ 8.6 Hz, 2H; 2CH biphenyl), 7.68 (d,
3J(H,H) ˆ 8.6 Hz, 2H; 2CH biphenyl), 8.68 (d, 3J(H,H) ˆ 8.1 Hz, 4H;
‡
‡
‡
‡
[M ], 192 (9) [M ‡H À Br], 191 (100) [M À Br], 190 (15) [M ‡H À Br],
‡
189 (52) [M À Br], 165 (7), 163 (2), 163 (5), 96 (13), 95 (16),83 (9), 82 (3).
Preparation of bichromophoric dyes by esterification; general procedure:
N-(sec-Alkyl)-N'-(2-hydroxyethyl)-perylene-3,4:9,10-tetracarboxylic bisi-
mide (0.49 mmol) in anhydrous pyridine (10 mL) and the corresponding
carboxylic chloride (0.83 mmol) were stirred (room temperature, drying
tube, 24 h). Ice water was added and the solution was briefly treated with
1n HCl, collected by vacuum filtration, washed with distilled water and
dried in air (1208C, 16 h). The reaction product was further purified by
column separation.
N-(1-Hexylheptyl)-N'-(2-ethyloxycarbonyl-2'-anthraquinonyl)-perylene-
3,4:9,10-tetracarboxylix bisimide (16a): N-(1-Hexylheptyl)-N'-(2-hydrox-
yethyl)-perylene-3,4:9,10-tetracarboxylic
bisimide
(8a)
(200 mg,
0.32 mmol) and anthraquinone-2-carboxylic chloride (180 mg, 0.67 mmol)
were allowed to react according to the general procedure and purified by
two column separations (silica gel, chloroform/acetone 15:1 and chloro-
form; broad, red band) to yield a bright red powder (100 mg, 37%). M.p.
280 2828C; Rf (silica gel/CHCl3) ˆ 0.07, Rf (silica gel, CHCl3/acetone
15:1) ˆ 0.69; IR (KBr): nÄ ˆ3070w, 2954m, 2927m, 2856m, 1730m, 1697s,
1678m, 1658s, 1594s, 1437m, 1405s, 1342s, 1295w, 1268s, 1245s, 1173w,
1110w, 811s, 746s, 708 cmÀ1 s; 1H NMR (400 MHz, CDCl3, 258C, TMS):
3
4CH perylene), 8.76 (d, J(H,H) ˆ 8.1 Hz, 4H; 4CH perylene); 13C NMR
(CDCl3): d ˆ 13.98 (2C, CH3), 22.54, 26.90, 29.17, 31.72, 32.37 (10C, CH2),
5636
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0947-6539/02/0824-5636 $ 20.00+.50/0
Chem. Eur. J. 2002, 8, No. 24

Bichromophoric Perylene Derivatives
5630 5643
d ˆ 0.83 (t, 6H; 2CH3), 1.31 (m, 16H; 8CH2), 1.89 (m, 2H; a-CH2), 2.23 (m,
2H; a-CH2), 4.71 (t, 3J(H,H) ˆ 5.0 Hz, 2H; CH2-OR), 4.82 (t, 3J(H,H) ˆ
5.3 Hz, 2H; CH2-NR'2), 5.18 (m, 1H; 1CH), 7.77 (m, 2H; 5-H and 8-H
anthraquinone), 8.26 (t, 3J(H,H) ˆ 4.9 Hz, 2H; 6-H and 7-H anthraqui-
none), 8.31 (d, 3J(H,H) ˆ 7.9 Hz, 1H; 3-H anthraquinone), 8.39 (dd,
3J(H,H) ˆ 8.0 Hz, 4J(H,H) ˆ 1.6 Hz, 1H; 2-H anthraquinon), 8.52 (d,
3J(H,H) ˆ 7.8 Hz, 2H; 2CH perylene), 8.54 (d, 3J(H,H) ˆ 7.9 Hz, 2H;
2CH perylene), 8.64 (d, 3J(H,H) ˆ 7.8 Hz, 4H; 4CH perylene), 8.84 (d,
4J(H,H) ˆ 1.5 Hz, 1H; 1-H anthraquinone); COSY NMR: cross-peaks at
d ˆ (7.77, 8.26), (8.31, 8.39), (8.39, 8.84); 13C NMR (CDCl3): d ˆ 14.08 (2C,
CH3), 22.63, 27.05, 29.09, 31.82, 32.41 (10C, CH2), 39.36 (1C, CH2-NR'2),
54.93 (1C, CH), 63.46 (1C, CH2-OR), 122.46, 122.83, 122.92, 125.65, 125.79,
127.18, 127.22, 127.42, 128.39, 128.97, 129.14, 131.04, 132.95, 133.17, 133.66,
134.25, 134.39, 134.76, 135.12, 135.72 (32C, CH perylene, CH anthraqui-
1282w, 1253w, 1191w, 1176w, 1139w, 811s, 747 cmÀ1 s; 1H NMR (400 MHz,
CDCl3, 258C, TMS): d ˆ 0.83 (t, 6H; 2CH3), 1.30 (m, 16H; 8CH2), 1.88 (m,
2H; a-CH2), 2.25 (m, 2H; a-CH2), 4.70 (t, 3J(H,H) ˆ 5.3 Hz, 2H; CH2-
3
OR), 4.80 (t, J(H,H) ˆ 5.3 Hz, 2H; CH2-NR'2), 5.19 (m, 1H; 1CH), 6.95
3
(d, 3J(H,H) ˆ 7.3 Hz, 1H; 5-H fluorenone), 6.98 (t, J(H,H) ˆ 7.3 Hz, 1H;
6-H fluorenone), 7.36 (dt, 3J(H,H) ˆ 7.3 Hz, 4J(H,H) ˆ 1.6 Hz, 1H; 7-H
f1uorenone), 7.44 (d, 3J(H,H) ˆ 7.5 Hz, 1H; 8-H f1uorenone), 7.51 (d,
3J(H,H) ˆ 7.9 Hz, 1H; 2-H or 4-H f1uorenone), 7.52 (d, 3J(H,H) ˆ 7.7 Hz,
1H; 2-H or 4-H fluorenone), 7.57 (dd, 3J(H,H) ˆ 8.4 Hz, 3J(H,H) ˆ 8.6 Hz,
1H; 3-H f1uorenone), 8.56 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.60
(d, 3J(H,H) ˆ 8.1 Hz, 4H; 4CH perylene), 8.63 (d, 3J(H,H) ˆ 8.1 Hz, 2H;
2CH perylene), 8.67 (brs, 2H; 1CH perylene); COSY NMR: cross-peaks
at d ˆ (6.98, 7.36), (7.36, 7.44), (7.52, 7.57); 13C NMR (CDCl3): d ˆ 14.01 (2C,
CH3), 22.56, 26.93, 29.20, 31.74, 32.37 (10C, CH2), 39.00 (1C, CH2-NR'2),
54.80 (1C, CH), 63.08 (1C, CH2-OR), 120.10, 122.28, 122.92, 123.02, 123.30,
124.08, 126.31, 126.45, 128.86, 129.10, 129.52, 129.57, 130.72, 131.21, 131.37,
ˆ
ˆ
none), 163.22, 164.88 (5C, C O perylene and ester), 182.00 (1C, C O
fluorenone); UV/Vis (CHCl3): lmax (e) ˆ 260 (80850), 275 (20990), 325
(9090), 370 (4160), 433 sh (5020), 459 (18050), 490 (50520), 527 nm
(84880); fluorescence (CHCl3): lmax (Irel) ˆ 535 (1.00), 577 (0.52), 626 nm
(0.12); fluorescence quantum yield (lexc ˆ 490 nm, E490 nm ˆ 0.0356/1 cm,
CHCl3, reference 1a with F ˆ 1.00) ˆ 1.00; MS (70 eV): m/z (%): 851 (4)
ˆ
133.37, 134.21, 134.52, 143.05, 144.82 (32C, Ar), 163.52, 166.73 (5C, C O
ˆ
perylene and ester), 190.66 (1C, C O f1uorenone); UV (CHCl3): lmax (e) ˆ
261 (85160), 370 (4800), 433 sh (5010), 459 (17340), 490 (48130), 527 nm
(80410); fluorescence (CHCl3): lmax (Irel) ˆ 534 (1.00), 577 nm (0.52), 625
(0.12); fluorescence quantum yield (lexc ˆ 490 nm, E490 nm ˆ 0.0311/1 cm,
‡
‡
‡
[M ‡H], 850 (7) [M ], 669 (12), 668 (24) [M À C13H26], 433 (11), 418 (7),
‡
417 (12), 391 (5), 390 (11) [M À C13H26 À C17H10O4], 373 (4), 345 (3), 253
CHCl3, reference 1a with F ˆ 1.00) ˆ 0.93; Solid-state fluorescence: lmax
ˆ
‡
(16), 252 (100), 236 (13), 235 (24), 224 (29); elemental analysis calcd (%)
for C54H46N2O8 (850.3): C 76.21, H 5.45, N 3.29; found: C 76.11, H 5.45, N
3.20.
618 nm br.; MS (70 eV): m/z (%): 823 (1), 822 (3) [M ], 642 (1), 641 (3), 640
‡
‡
(2) [M À C13H26], 391 (1), 390 (2) [M À C13H26 À C16H11O3], 224 (28)
‡
‡
[C14H8O3 ], 208 (4), 207 (2) [C14H7O2 ], 181 (18), 180 (100), 179 (1), 152
(30), 151 (20), 150 (13); elemental analysis calcd (%) for C53H46N2O7
(823.0): C 77.35, H 5.63, N 3.40; found: C 77.20, H 5.53, N 3.40.
N-(1-Heptyloctyl)-N'-(2-ethyloxycarbonyl-2'-anthraquinonyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (16b): N-(1-Heptyloctyl)-N'-(2-hydrox-
yethyl)-perylene-3,4:9,10-tetracarboxylic bisimide (8b, 260 mg, 0.40 mmol)
and anthraquinone-2-carboxylic chloride (200 mg, 0.74 mmol) were al-
lowed to react according to the general procedure and purified by two
column separations (silica gel, chloroform/acetone 15:1 and chloroform;
broad, red band) to yield a bright red powder (320 mg, 91%). M.p. 274
2778C; Rf (silica gel, CHCl3/acetone 15:1) ˆ 0.72, Rf (silica gel/CHCl3) ˆ
0.11; IR (KBr): nÄ ˆ2926m, 2855m, 1728m, 1697s, 1678m, 1658s, 1595s,
1579m, 1437m, 1405s, 1343s, 1295w, 1268m, 1246m, 1173w, 1110w, 811s,
746s, 707 cmÀ1 s; 1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.83 (t, 6H;
2CH3), 1.30 (m, 20H; 10CH2), 1.91 (m, 2H; a-CH2), 2.23 (m, 2H; a-CH2),
4.71 (t, 3J(H,H) ˆ 5.0 Hz, 2H; CH2-OR), 4.83 (t, 3J(H,H) ˆ 4.7 Hz, 2H;
CH2-NR'2), 5.17 (m, 1H; 1CH), 7.75 (m, 2H; 5-H and 8-H anthraquinone),
8.24 (t, 3J(H,H) ˆ 5.7 Hz, 2H; 6-H and 7-H anthraquinone), 8.28 (d,
3J(H,H) ˆ 7.9 Hz, 1H; 3-H anthraquinone), 8.39 (dd, 3J(H,H) ˆ 8.1 Hz,
4J(H,H) ˆ 1.7 Hz, 1H; 2-H anthraquinone), 8.47 (d, 3J(H,H) ˆ 8.1 Hz, 2H;
2CH perylene), 8.50 (d, 3J(H,H) ˆ 8.4 Hz, 2H; 2CH perylene), 8.60 (d,
N-(1-Hexylheptyl)-N'-(2-ethyloxycarbonyl-2-fluorene-9-onyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (16d): N-(1-Hexylheptyl)-N'-(2-hydrox-
yethyl)-perylene-3,4:9,10-tetracarboxylic
bisimide
(8a)
(300 mg,
0.49 mmol) and fluorene-9-one-2-carboxylic chloride (200 mg, 0.83 mmol)
were allowed to react according to the general procedure and purified by
column separation (silica gel, chloroform/acetone 15:1 to yield a red
powder (100 mg, 24%). M.p. 275 2778C; Rf (silica gel, CHCl3/acetone
15:1) ˆ 0.50; IR (KBr): nÄ ˆ3070w), 2956m, 2927m, 2857m, 1720m, 1697s,
1658s, 1618w, 1595s, 1579w, 1458w, 1439w, 1405m, 1343s, 1286w, 1253s,
1184w, 1112w, 811s, 746s, 668 cmÀ1 m; 1H NMR (400 MHz, CDCl3, 258C,
TMS): d ˆ 0.84 (t, 6H; 2CH3), 1.31 (m, 16H; 8CH2), 1.88 (m, 2H; a-CH2),
2.25 (m, 2H; a-CH2), 4.66 (s, 2H; CH2-OR), 4.77 (s, 2H; CH2-NR'2), 5.16
(m, 1H; 1CH), 7.36 (t, 3J(H,H) ˆ 7.4 Hz, 1H; 7-H fluorenone), 7.53 (t,
3J(H,H) ˆ 7.4 Hz, 1H; 6-H fluorenone), 7.55 (m, 2H; 5-H and 4-H
fluorenone), 7.69 (d, 3J(H,H) ˆ 7.4 Hz, 1H; 8-H fluorenone), 8.17 (dd,
3J(H,H) ˆ 7.6 Hz, 4J(H,H) ˆ 1.5 Hz, 1H; 3-H fluorenone), 8.20 (s, 1H; 1-H
fluorenone), 8.63 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.64 (d,
3J(H,H) ˆ 8.1 Hz, 4H; 4CH perylene), 8.73 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH
perylene); 13C NMR (CDCl3): d ˆ 14.16 (2C, CH3), 22.70, 27.22, 29.35,
31.89, 32.40 (10C, CH2), 39.36 (1C, CH2-NR'2), 54.88 (1C, CH), 62.82 (1C,
CH2-OR), 119.59, 120.54, 121.98, 122.40, 122.75, 124.35, 124.90, 128.27,
128.63, 130.04, 130.43, 131.00, 133.01, 133.28, 133.66, 134.11, 134.53, 136.23,
4
3J(H,H) ˆ 7.8 Hz, 4H; 4CH perylene), 8.81 (d, J(H,H) ˆ 1.3 Hz, 1H; 1-H
anthraquinone); COSY NMR: cross-peaks at d ˆ (7.75, 8.24), (8.28, 8.39),
(8.39, 8.81); 13C NMR (CDCl3): d ˆ 14.04 (2C, CH3), 22.60, 27.04, 29.22,
29.52, 31.80, 32.37 (12C, CH2), 39.24, (1C, CH2-NR2'), 54.86 (1C, CH),
63.36 (1C, CH2-OR), 122.67, 122.98, 123.03, 126.00, 126.19, 127.26, 127.28,
127.45, 128.61, 129.28, 129.32, 131.40, 133.15, 133.21, 133.34, 133.97, 134.28,
134.38, 134.65, 134.69, 135.12, 135.88 (32C, CH perylene, CH anthraqui-
ˆ
142.76, 147.75 (32C, Ar), 162.84, 165.24 (5C, C O perylene and ester),
ˆ
ˆ
ˆ
none), 163.39, 164.91 (C O, 5C perylene and ester), 182.06, 182.25 (C O,
2C anthraquinone); UV (CHCl3): lmax (e) ˆ 260 (84720), 275 (31020), 325
(9680), 371 (4360), 433 sh (5140), 459 (17970). 490 (49750), 527 nm
(83420); fluorescence (CHCl3): lmax (Irel) ˆ 535 (1.00), 577 (0.52), 625 nm
(0.12); fluorescence quantum yield (lexc ˆ 490 nm, E490 nm ˆ 0.0311/1 cm,
CHCl3, reference 1a with F ˆ 1.00) ˆ 0.95; MS (70 eV): m/z (%): 879 (5)
192.28 (1C, C O fluorenone); UV (CHCl3): lmax (e) ˆ 261 (83690), 271
(80840), 299 (9240), 315 (6760), 370 (4910), 434 sh (5200), 456 (18000), 490
(49850), 527 nm (83800); fluorescence (CHCl3): lmax (Irel) ˆ 535 (1), 577
‡
(0.52), 625 nm (0.12); MS (70 eV): m/z (%): 823 (8), 822 (14) [M ], 805 (8),
‡
‡
642 (7), 641 (25), 640 (52) [M À C13H26], 616 (5), 615 (12) [M À C14H7O2],
‡
598 (12) [M À C14H8O3], 435 (8), 434 (10), 433 (28), 418 (16), 417 (33), 416
‡
‡
‡
‡
[M ‡H], 878 (9) [M ], 669 (10), 668 (22) [M À C15H30], 433 (12), 418 (10),
(12), 415 (10), 391 (15), 390 (32) [M À C13H26 À C16H11O3], 373 (15), 345
‡
‡
‡
417 (16), 391 (7), 390 (16) [M À C15H30 À C17H10O4], 373 (7), 345 (4), 253
(10), 224 (29) [C14H8O3 ], 208 (61), 207 (100) [C14H7O2 ], 179 (24)
‡
‡
(17), 252 (100), 236 (16), 235 (18), 224 (36); elemental analysis calcd (%)
for C56H50N2O8 (879.0): C 76.52, H 5.73, N 3.19; found: C 76.23, H 5.71, N
3.28.
[C13H7O ], 151 (23) [C12H7 ]; elemental analysis calcd (%) for C53H46N2O7
(823.0): C 77.35, H 5.63, N 3.40; found: C 76.87, H 5.89, N 3.50.
N-(1-Heptyloctyl)-N'-(2-ethyloxycarbonyl-2-fluorene-9-onyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (16e): N-(1-Heptyloctyl)-N'-(2-hydrox-
yethyl)-perylene-3,4:9,10-tetracarboxylic bisimide (8b, 280 mg, 0.43 mmol)
and fluorene-9-one-2-carboxylic chloride (210 mg, 0.87 mmol) were al-
lowed to react according to the general procedure and purified by two
column separations (silica gel, chloroform/acetone 15:1 and chloroform;
violet band) to yield a red powder (200 mg, 55%). M.p. 265 2678C; Rf
(silica gel, CHCl3/acetone 15:1) ˆ 0.61, Rf (silica gel/CHCl3) ˆ 0.17; IR
(KBr): nÄ ˆ3070w, 2956m, 2927m, 2855m, 1718s, 1697s, 1658s, 1595s,
1457w, 1437w, 1405m, 1343s, 1286w, 1252s, 1111w, 810s, 746 cmÀ1 s;
1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.82 (t, 6H; 2CH3), 1.27 (m,
N-(1-Hexylheptyl)-N'-(2-ethyloxycarbonyl-1-fluorene-9-onyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (16c): N-(1-Hexylheptyl)-N'-(2-hydrox-
yethyl)-perylene-3,4:9,10-tetracarboxylic
bisimide
(8a)
(100 mg,
0.16 mmol) and fluorene-9-one-1-carboxylic chloride (80 mg, 0.33 mmol)
were allowed to react according to the general procedure and purified by
column separation (silica gel, chloroform/acetone 15:1), extraction with
cyclohexane and extractive recrystallization from toluene to yield a red
powder with solid-state fluorescence (90 mg, 68%). M.p. 276 2788C; Rf
(silica gel, CHCl3/acetone 15:1) ˆ 0.46; IR (KBr): nÄ ˆ3070brw, 2955m,
2926m, 2856m, 1720w, 1697s, 1658s, 1595s, 1438w, 1405m, 1343s, 1300w,
Chem. Eur. J. 2002, 8, No. 24
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0947-6539/02/0824-5637 $ 20.00+.50/0
5637

H. Langhals and S. Saulich
FULL PAPER
20H; 10CH2), 1.87 (m, 2H; a-CH2), 2.24 (m, 2H; a-CH2), 4.71 (t, 2H; CH2-
OR), 4.73 (brs, 2H; CH2-NR'2), 5.18 (m, 1H; 1CH), 7.35 (t, 3J(H,H) ˆ
7.5 Hz, 1H; 7-H fluorenone), 7.51 (t, 3J(H,H) ˆ 7.3 Hz, 1H; 6-H fluore-
none), 7.55 (m, 2H; 5-H and 4-H fluorenone), 7.67 (d, 3J(H,H) ˆ 7.5 Hz,
1H; 8-H fluorenone), 8.19 (dd, 3J(H,H) ˆ 7.5 Hz, 4J(H,H) ˆ 1.5 Hz, 1H;
3-H fluorenone), 8.20 (s, 1H; 1-H fluorenone), 8.58 (d, 3J(H,H) ˆ 7.2 Hz,
4H; 4CH perylene), 8.70 (d, 3J(H,H) ˆ 8.1 Hz, 4H; 4CH perylene);
13C NMR(CDCl3): d ˆ 14.10 (2C, CH3), 22.67, 27.17, 29.30, 29.59, 31.88,
32.39 (12C, CH2), 39.30 (1C, CH2-NR'2), 54.87 (1C, CH), 62.84 (1C, CH2-
OR), 119.80, 120.74, 122.34, 122.71, 122.98, 124.42, 125.12, 125.43, 128.74,
128.96, 130.07, 130.36, 131.04, 133.48, 133.85, 134.35, 134.65, 134.78, 136.33,
1183w, 1112w, 811s, 748 cmÀ1 s; 1H NMR (400 MHz, CDCl3, 258C, TMS):
d ˆ 1.27 (s, 9H; 1C(CH3)3), 1.32 (s, 9H; 1C(CH3)3), 4.70 (brs, 4H; R'2N-
CH2-CH2-OR), 7.08 (d, 4J(H,H) ˆ 2.1 Hz, 1H; 6-H phenyl), 7.35 (dt,
3J(H,H) ˆ 7.4 Hz, 4J(H,H) ˆ 1.2 Hz, 1H; 7-H fluorenone), 7.46 (dd,
3J(H,H) ˆ 8.6 Hz, 4J(H,H) ˆ 2.1 Hz, 1H; 4-H phenyl), 7.51 (t, 3J(H,H) ˆ
7.4 Hz, 1H; 6-H fluorenone), 7.56 (m, 2H; 5-H and 4-H fluorenone), 7.58 (d,
3J(H,H) ˆ 8.5 Hz, 1H; 3-H phenyl), 7.67 (d, 3J(H,H) ˆ 7.5 Hz, 1H; 8-H
fluorenone), 8.18 (dd, 3J(H,H) ˆ 9.8 Hz, 4J(H,H) ˆ 1.7 Hz, 1H; 3-H fluo-
renone), 8.19 (d, 4J(H,H) ˆ 1.2 Hz, 1H; 1-H fluorenone), 8.62 (d,
3J(H,H) ˆ 8.2 Hz, 2H; 2CH perylene), 8.63 (d, 3J(H,H) ˆ 8.1 Hz, 2H;
2CH perylene), 8.70 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.72 (d,
3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene); 13C NMR (CDCl3): d ˆ 31.23 (3C,
CH3), 31.74 (3C, CH3), 34.29 (1C, C(CH3)3), 35.53 (1C, C(CH3)3), 39.20
(1C, CH2-NR'2), 62.72 (1C, CH2-OR), 120.15, 121.15, 123.06, 123.27, 123.32,
123.74, 124.56, 125.49, 126.35, 126.56, 127.79, 128.79, 129.51, 129.84, 130.14,
130.98, 131.72, 131.82, 132.58, 134.17, 134.78, 134.87, 134.91, 136.50, 143.32,
ˆ
142.97, 147.97 (32C, aryl), 163.12, 165.33 (5C, C O perylene and ester),
ˆ
192.40 (1C, C O fluorenone); UV (CHCl3): lmax (e) ˆ 261 (83670), 271
(80840), 299 (9150), 369 (4960), 433 sh (5390), 459 (18020), 490 (49200),
527 nm (82080); fluorescence (CHCl3): lmax (Irel) ˆ 533 (1.00), 577 (0.52),
624 nm (0.12); fluorescence quantum yield (lexc ˆ 490 nm, E490 nm ˆ 0.0311/
1 cm, CHCl3, reference 1a with F ˆ 1.00) ˆ 0.96; MS (70 eV): m/z (%): 851
ˆ
143.76, 148.36, 150.19 (38C, aryl), 163.51, 164.36, 165.41 (5C, C O perylene
‡
‡
ˆ
(18), 850 (33) [M ], 834 (10), 833 (17), 643 (25) [M À C14H7O2], 642 (12),
and ester), 192.56 (1C, C O fluorenone); UV (CHCl3): lmax (e) ˆ 262
‡
‡
641 (48), 640 (100) [M À C15H3O], 627 (10), 626 (20) [M À C14H8O3], 435
(85990), 271 (80260), 299 (10060), 315 (6150), 369 (5600), 433 sh (6100),
459 (19370), 491 (52590), 527 nm (88100); fluorescence (CHCl3): lmax
(Irel) ˆ 534 (1.00), 576 (0.52), 525 nm (0.12); fluorescence quantum yield
(lexc ˆ 490 nm, E490 nm ˆ 0.0374/1 cm, CHCl3, reference 1a with F ˆ 1.00) ˆ
(11), 434 (12), 433 (35), 418 (20), 417 (40), 416 (15), 415 (11), 391 (14), 390
‡
‡
(34) [M À C15H3O À C16H11O3], 373 (15), 345 (10), 224 (9) [C14H8O3 ], 208
‡
‡
(59), 207 (87) [C14H8O2 ], 180 (17), 179 (16), 151 (14) [C12H7 ]; elemental
analysis calcd (%) for C55H50N2O7 (851.0): C 77.63, H 5.92, N 3.29; found: C
77.68, H 6.03, N 3.20.
‡
0.98; MS (70 eV): m/z (%): 828 (1) [M ], 774 (1), 773 (12), 772 (45), 771
‡
(76) [M À C4H9], 608 (3), 607 (9), 549 (5), 547 (2), 419 (2), 390 (3), 225
‡
‡
(13), 224 (100) [C14H8O3 ], 208 (6), 207 (48) [C14H7O2 ], 179 (16) [C13H7O],
151 (33) [C12H7]; elemental analysis calcd (%) for C54H40N2O7 (828.9): C
78.25, H 4.86, N 3.38; found: C 77.89, H 4.97, N 3.36.
N-(1-Hexylheptyl)-N'-(2-ethyloxycarbonyl-4'-fluorene-9-onyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (16 f): N-(1-Hexylheptyl)-N'-(2-hydrox-
yethyl)-perylene-3,4:9,10-tetracarboxylic
bisimide
(8a)
(200 mg,
0.32 mmol) and fluorene-9-one-4-carboxylic chloride (170 mg, 0.71 mmol)
were allowed to react according to the general procedure and purified by
two column separations (silica gel, chloroform/acetone 15:1 and silica gel,
chloroform) to yield a reddish orange powder with solid-state fluorescence
(200 mg, 76%). M.p. 239 2418C; Rf (silica gel, CHCl3/acetone 15:1) ˆ 0.67,
Rf (silica gel, CHCl3) ˆ 0.12; IR (KBr): nÄ ˆ2956w, 2927m, 2860w, 1720w,
1696s, 1658s, 1595s, 1405m, 1343s, 1248m, 810s, 746 cmÀ1 s; 1H NMR
(400 MHz, CDCl3, 258C, TMS): d ˆ 0.82 (t, 6H; 2CH3), 1.30 (m, 16H;
8CH2), 1.87 (m, 2H; a-CH2), 2.25 (m, 2H; a-CH2), 4.72 (t, 3J(H,H) ˆ
N-(1-Hexylheptyl)-N'-(4-benzyloxycarbonyl-2'-anthraquinonyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (14a): N-(1-Hexylheptyl)-N'-(4-hydroxy-
methyl-phenyl)-perylene-3,4:9,10-tetracarboxylic bisimide (6a, 100 mg,
0.15 mmol) and anthraquinone-2-carboxyl chloride (80 mg, 0.30 mmol)
were allowed to react according to the general procedure and purified by
two column separations (silica gel, chloroform/acetone 15:1 and Al2O3
N II, chloroform; broad, orange band) to yield a red powder (50 mg, 37%).
M.p. 339 3428C; Rf (silica gel, CHCl3/acetone 15:1) ˆ 0.76; IR (KBr): nÄ
ˆ3070w, 2928m, 2856m, 1710m, 1698s, 1660s, 1594s, 1434w, 1405m,
1343s, 1268m, 1247m, 1174w, 811m, 747m, 708 cmÀ1 m; 1H NMR
(400 MHz, CDCl3, 258C, TMS): d ˆ 0.81 (t, 6H; 2CH3), 1.27 (m, 16H;
8CH2), 1.87 (m, 2H; a-CH2), 2.22 (m, 2H; a-CH2), 5.17 (m, 1H; 1CH), 5.53
(s, 2H; CH2-OR), 7.42 (d, 3J(H,H) ˆ 8.6 Hz, 2H; 2CH phenyl), 7.70 (d,
3J(H,H) ˆ 8.6 Hz, 2H; 2CH phenyl), 7.81 (m, 2H; 5-H und 8-H anthra-
quinone), 8.31 (m, 2H; 6-H and 7-H anthraquinone), 8.28 (d, 3J(H,H) ˆ
8.1 Hz, 1H; 3-H anthraquinone), 8.44 (dd, 3J(H,H) ˆ 8.1 Hz, 4J(H,H) ˆ
1.8 Hz, 1H; 2-H anthrachinone), 8.60 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH
perylene), 8.60 (d, 3J(H,H) ˆ 8.4 Hz, 2H; 2CH perylene), 8.64 (brs, 2H;
2CH perylene), 8.70 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.96 (d,
4J(H,H) ˆ 1.8 Hz, 1H; 1-H anthraquinone); 13C NMR (CDCl3): d ˆ 14.03
(2C, CH3), 22.57, 26.94, 29.20, 31.75, 32.37 (10C, CH2), 54.84 (1C, CH),
66.92 (1C, CH2-OR), 123.05, 123.17, 123.34, 126.39, 126.66, 127.38, 127.45,
127.58, 128.76, 129.04, 129.53, 131.88, 133.36, 133.43, 133.56, 134.22, 134.36,
134.46, 134.62, 135.02, 135.20, 136.11, 136.15 (38C, CH perylene, CH
3
5.2 Hz, 2H; CH2-OR), 4.82 (t, J(H,H) ˆ 5.3 Hz, 2H; CH2-NR'2), 5.17 (m,
1H; 1CH), 7.17 (dt, 3J(H,H) ˆ 7.4 Hz, 4J(H,H) ˆ 1.0 Hz, 1H; 1CH, 6-H
fluorenone), 7.29 (dt, 3J(H,H) ˆ 7.5 Hz, 4J ˆ 1.3 Hz, 1H; 1CH 7-H fluo-
renone), 7.31 (t, 3J(H,H) ˆ 7.3 Hz, 1H; 1CH, 2-H fluorenone), 7.57 (d,
3J(H,H) ˆ 7.4 Hz, 1H; 1CH, 5-H fluorenone), 7.77 (dd, 3J(H,H) ˆ 7.3 Hz,
4J(H,H) ˆ 1.3 Hz, 1H; 1CH, 1 or 3-H fluorenone), 7.95 (dd, 3J(H,H) ˆ
7.9 Hz, 4J(H,H) ˆ 1.3 Hz, 1H; 1CH,
1 or 3-H fluorenone), 8.17 (d,
3J(H,H) ˆ 7.7 Hz, 1H; CH, 8-H fluorenone), 8.52 (d, 3J(H,H) ˆ 8.2 Hz,
2H; 2CH perylene), 8.55 (d, 3J(H,H) ˆ 8.2 Hz, 4H; 2CH perylene), 8.60
3
(d, J(H,H) ˆ 8.0 Hz, 2H; 2CH perylene), 8.64 (brs, 2H; 2CH perylene);
COSY NMR: cross-peaks at d ˆ (7.17, 7.29), (7.17, 7.57), (7.29, 8.17),
(7.31,7.95,7.77); 13C NMR (CDCl3): d ˆ 14.03 (2C, CH3), 22.58, 26.94, 29.21,
31.75, 32.37 (10C, CH2), 39.26 (1C, CH2-NR'2), 54.84 (1C, CH), 62.77 (1C,
CH2-OR), 122.77, 122.93, 123.24, 123.87, 126.17, 126.28, 126.52, 126.65,
127.21, 128.55, 129.48, 131.59, 134.12, 134.25, 134.93, 135.02, 135.45, 136.30,
ˆ
ˆ
142.96, 144.14 (32C, aryl), 163.49, 166.41 (5C, C O perylene and ester),
anthraquinone, CH phenyl), 163.49, 164.78 (5C, C O perylene and ester),
ˆ
ˆ
192.80 (1C, C O fluorenone); UV (CHCl3): lmax (e) ˆ 262 (77790), 272
182.11, 182.51 (2C, C O anthraquinone); UV/Vis (CHCl3): lmax (e) ˆ 260
(48980), 306 (14030), 371 (8330), 435 sh (8500), 460 (22440), 491 (57370),
527 nm (93880); fluorescence (CHCl3): lmax (Irel) ˆ 535 (1.00), 577 (0.52),
626 nm (0.12); fluorescence quantum yield (lexc ˆ 490 nm, E490 nm ˆ 0.0311/
1 cm, CHCl3, reference 1a with F ˆ 1.00) ˆ 0.95. Solid-state fluorescence:
(86250), 275 sh (21990), 327 (9090), 368 (4410), 434 sh (5420), 459 (18920),
490 (52450), 527 nm (87450); fluorescence (CHCl3): lmax (Irel) ˆ 535 (1.00),
578 (0.52), 627 nm (0.12); fluorescence quantum yield (lexc ˆ 490 nm,
E490 nm ˆ 0.0311/1 cm, CHCl3, reference 1a with F ˆ 1.00) ˆ 0.99; MS
‡
‡
‡
lmax ˆ 614 nm br.; MS (70 eV): m/z (%): 823 (6), 822 (9) [M ], 805 (3), 641
(70 eV): m/z (%): 913 (11) [M ‡H], 912 (18) [M ], 895 (6), 732 (14),
‡
‡
‡
(11), 640 (21) [M À C13H26], 615 (2) [M À C14H7O2], 433 (10), 418 (7), 417
731 (37), 730 (48) [M À C13H26], 496 (10), 495 (25), 494 (13), 481 (11), 480
‡
(11), 416 (2), 391 (5), 390 (10) [M À C13H26 À C16H11O3], 373 (4), 345 (3),
(19), 479 (8), 373 (27), 345 (6), 253 (19), 252 (100), 236 (10), 235 (22), 224
(29), 182 (16); elemental analysis calcd (%) for C59H48N2O8 Â H2O (931.5):
C 76.11, H 5.41, N 3.01; found: C 76.32, H 5.52, N 3.00.
‡
‡
‡
224 (100) [C14H8O3 ], 208 (7), 207 (33) [C14H7O2 ], 179 (23) [C13H7O ], 151
‡
(22) [C12H7 ]; elemental analysis calcd (%) for C53H46N2O7 (823.0): C 77.35,
H 5.63, N 3.40; found: C 77.41, H 5.63, N 3.11.
N-(1-Hexylheptyl)-N'-(4-benzyloxycarbonyl-2'-fluorene-9-onyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (14b): N-(1-Hexylheptyl)-N'-(4-hydrox-
ymethyl-phenyl)-perylene-3,4:9,10-tetracarboxylic bisimide (6a, 100 mg,
0.15 mmol) and fluorene-9-one-2-carboxylic acid chloride (70 mg,
0.30 mmol) were allowed to react according to the general procedure and
purified by column separation (silica gel, chloroform/acetone 15:1; broad,
orange band) to yield a red powder (120 mg, 90%). M.p. 292 2948C; Rf
(silica gel, CHCl3/acetone 15:1) ˆ 0.60; IR (KBr): nÄ ˆ3070w, 2954w,
2976m, 2856m, 1711s, 1698s, 1658s, 1617w, 1594s, 1579m, 1433w, 1405m,
N-(2,5-Di-tert-butyl-phenyl)-N'-(2-ethyloxycarbonyl-2'-fluorene-9-onyl)-
perylene-3,4:9,10-tetracarboxylic bisimide (16g): N-(2,5-Di-tert-butyl-phe-
nyl)-N'-(2-hydroxyethyl)-perylene-3,4:9,10-tetracarboxylic bisimide (8d,
50 mg, 0.08 mmol) and fluorene-9-one-2-carboxylic acid chloride (0.66 g,
0.16 mmol) were allowed to react according to the general procedure to
yield a red solid (40 mg, 60%). M.p. >3508C; Rf (silica gel, CHCl3/acetone
15:1) ˆ 0.25; IR (KBr): nÄ ˆ3080w, 2964m, 2927m, 1701 (brm), 1697s,
1664s, 1617w, 1594s, 1457w, 1437w, 1404m, 1356m, 1346s, 1285w, 1252s,
5638
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0947-6539/02/0824-5638 $ 20.00+.50/0
Chem. Eur. J. 2002, 8, No. 24

Bichromophoric Perylene Derivatives
5630 5643
1343s, 1285w, 1254s, 1177w, 1123w, 1110w, 811m, 746 cmÀ1 m; 1H NMR
(400 MHz, CDCl3, 258C, TMS): d ˆ 0.81 (t, 6H; 2CH3), 1.26 (m, 16H;
8CH2), 1.85 (m, 2H; a-CH2), 2.25 (m, 2H; a-CH2), 5.17 (m, 1H; 1CH), 5.48
(s, 2H; CH2-OR), 7.37 (dt, 3J(H,H) ˆ 7.4 Hz, 4J(H,H) ˆ 1.1 Hz, 1H; 7-H
fluorenone), 7.39 (d, 3J(H,H) ˆ 8.4 Hz, 2H; 2CH phenyl), 7.53 (dt,
3J(H,H) ˆ 7.5 Hz, 4J(H,H) ˆ 1.2 Hz, 1H; 6-H fluorenone), 7.53 (d,
3J(H,H) ˆ 7.2 Hz, 1H; 5-H fluorenone), 7.61 (d, 3J(H,H) ˆ 7.8 Hz, 1H;
4-H fluorenone), 7.67 (d, 3J(H,H) ˆ 8.5 Hz, 2H; 2CH phenyl), 7.71 (d,
3J(H,H) ˆ 7.4 Hz, 1H; 8-H fluorenone), 8.26 (dd, 3J(H,H) ˆ 7.7 Hz,
4J(H,H) ˆ 1.5 Hz, 1H; 3-H fluorenone), 8.35 (d, 4J(H,H) ˆ 1.6 Hz, 1H;
1-H fluorenone), 8.64 (d, 3J(H,H) ˆ 8.2 Hz, 2H; 2CH perylene), 8.65 (d,
3J(H,H) ˆ 8.2 Hz, 2H; 2CH perylene), 8.69 (brs, 2H; 2CH perylene), 8.73
(d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene); 13C NMR (CDCl3): d ˆ 14.04
(2C, CH3), 22.58, 26.93, 29.21, 31.76, 32.38 (10C, CH2), 66.42 (1C, CH2-
OR), 120.22, 121.21, 123.09, 123.37, 124.64, 125.46, 128.95, 129.38, 130.19,
130.92, 131.94, 135.26, 136.51 (38C, CH perylene, CH fluorenone, CH
0.73; IR (KBr): nÄ ˆ3070w, 2954m, 2927m, 2857m, 1735w, 1697s, 1660s,
1595s, 1579w, 1533w, 1437w, 1405m, 1343s, 1292w, 1252w, 1210w, 1176w,
811m, 747m, 714 cmÀ1 m; 1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ
0.84 (t, 6H; 2CH3), 1.31 (m, 16H; 8CH2), 1.91 (m, 2H; a-CH2), 2.27 (m,
2H; a-CH2), 3.61 (m, 1H; 1NH), 4.65 (s, 2H; CH2-OR), 4.73 (s, 2H; CH2-
NR'2), 5.21 (m, 1H; 1CH), 7.60 (m, 3H; 3CH anthraquinone), 7.83 (m, 1H;
1CH anthraquinone), 7.94 (m, 1H; 1-H anthraquinone), 8.04 (m, 2H; 2CH
anthraquinone), 8.43 8.63 (m, 8H; 8CH perylene); UV/Vis (CHCl3): lmax
(e) ˆ 261 (51290), 276 (36590), 286 sh (33350), 371 (8590), 434 (5520), 461
(16240), 491 (43890), 528 nm (71590); fluorescence (CHCl3): lmax (Irel) ˆ
538 (1.00), 580 (0.56), 620 nm (0.14); fluorescence quantum yield (lexc
ˆ
491 nm, E491 nm ˆ 0.0311/1 cm, CHCl3, reference 1a with F ˆ 1.00) ˆ 0.96;
‡
‡
‡
MS FAB (3-NBA): m/z (%): 867 (3) [M ‡H], 866 (3) [M ], 617 (2) [M
À
C15H7NO3], 615 (5), 601 (7), 600 (31), 599 (70), 598 (7), 597 (7), 513 (4), 419
‡
(15), 418 (52), 417 (100) [M À C15H7NO3-C13H26-H2O], 391 (15), 390 (11),
375 (11), 373 (23), 345 (14); elemental analysis calcd (%) for C54H47N3O8
(866.0): C 74.90, H 5.47, N 4.85; found: C 74.26, H 5.52, N 5.03.
ˆ
ˆ
phenyl), 163.55 (5C, C O perylene and ester), 177.02 (1C, C O fluore-
none); UV (CHCl3): lmax (e) ˆ 261 (85380), 271 (83080), 299 (8140), 315
(5390), 369 (4310), 435 sh (4530), 459 (17160), 490 (48700), 527 nm
(82100); fluorescence (CHCl3): lmax (Irel) ˆ 535 (1.00), 577 (0.52), 626 nm
(0.12); fluorescence quantum yield (lexc ˆ 490 nm, E490 nm ˆ 0.0311/1 cm,
CHCl3, reference 1a with F ˆ 1.00) ˆ 0.97; MS (70 eV): m/z (%): 885 (11)
N-(1-Heptyloctyl)-N'-(2-ethylcarbamyl-N-(2'-anthraquinonyl))-perylene-
3,4:9,10-tetracarboxylic bisimide (12b): Anthraquinone-2-isocyanate
(110 mg, 0.44 mmol), N-(1-heptyloctyl)-N'-(2-hydroxyethyl)-perylene-
3,4:9,10-tetracarboxdiimide (8b, 210 mg, 0.33 mmol) and anhydrous tol-
uene (20 mL) were heated under reflux under Ar for 18 h (change in colour
from dark red to light orange after 30 min), cooled to room temperature,
collected by vacuum filtration (D4), washed with chloroform/ethanol 20:1
and ethanol, dried at 1308C for 16 h (bright orange material), and
extractively recrystallized from chloroform to yield a bright orange powder
with an intense solid-state fluorescence (190 mg, 64%). M.p. 280 2828C;
Rf (silica gel, CHCl3/ethanol 10:1) ˆ 0.50; IR (KBr): nÄ ˆ 3320m (NH),
3070w, 2954s, 2926s, 2855s, 1742m, 1697s, 1659s, 1594s, 1579w, 1535m,
1438m, 1405s, 1343s, 1293w, 1251m, 1209m, 1176w, 1060w, 811s, 747m,
721w, 714 cmÀ1 m; 1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.82 (t,
6H; 2CH3), 1.27 (m, 20H; 10CH2), 1.90 (m, 2H; a-CH2), 2.26 (m, 2H; a-
‡
‡
‡
[M ‡H], 884 (21) [M ], 867 (2), 704 (10), 703 (27), 702 (30) [M À C13H26],
662 (2), 629 (5), 628 (11), 496 (3), 495 (12), 481 (5), 480 (11), 479 (7), 419
(12), 418 (19), 390 (6), 373 (31), 224 (12), 223 (100), 207 (17), 206 (69);
elemental analysis calcd (%) for C58H47N2O7 (884.0): calcd for C 78.80, H
5.36, N 3.17; found: C 78.27, H 5.42, N 3.09; elemental analysis calcd (%) for
C58H47N2O7: 884.3461; found: 884.3481 (HRMS).
N-(1-Hexylheptyl)-N'-(2-ethylcarbamyl-N-(1'-naphthyl))-perylene-
3,4:9,10-tetracarboxylic bisimide (12c): 1-Naphthylisocyanate (170 mg,
1.00 mmol), N-(1-hexylheptyl)-N'-(2-hydroxyethyl)-perylene-3,4:9,10-tet-
racarboxylic bisiimide (8a, 300 mg, 0.41 mmol) and anhydrous toluene
(15 mL) were heated under reflux under Ar for 3 h, evaporated in vacuo,
dried (1208C), purified by column separation (Al2O3 N II, chloroform/
ethanol 20:1) and by extractive recrystallization from chloroform to yield a
reddish brown powder (210 mg, 65%). M.p. 232 2348C; Rf (Al2O3 N II,
CHCl3/ethanol 20:1) ˆ 0.43, Rf (silica gel, CHCl3/ethanol 20:1) ˆ 0.29; IR
(KBr): nÄ ˆ3350 (NH)w, 3070w, 2955s, 2928s, 2856s, 1694brs, 1658s, 1594s,
1579w, 1537m, 1501m, 1438m, 1405s, 1343s, 1253m, 1213m, 1176w, 811s,
794m, 776m, 747 cmÀ1 m; 1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ
0.84 (t, 6H; 2CH3), 1.29 (m, 16H; 8CH2), 1.85 (m, 2H; a-CH2), 2.22 (m,
2H; a-CH2), 4.58 (t, 3J(H,H) ˆ 4.2 Hz, 2H; CH2-OR), 4.66 (t, 3J(H,H) ˆ
4.1 Hz, 2H; CH2-NR'2), 5.14 (m, 1H; 1CH), 7.37 (t, 3J(H,H) ˆ 7.8 Hz, 1H;
1CH naphthalene), 7.47 (t, 3J(H,H) ˆ 8.5 Hz, 2H; 2CH naphthalene), 7.59
(d, 3J(H,H) ˆ 8.0 Hz, 1H; 1CH naphthalene), 7.79 (m, 2H; 2CH naph-
thalene), 8.01 (d, 3J(H,H) ˆ 8.4 Hz, 1H; 1CH naphthalene), 8.13 (d,
J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.20 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH
perylene), 8.40 (d, 3J(H,H) ˆ 7.8 Hz, 2H; 2CH perylene), 8.49 (brs, 2H;
2CH perylene); 13C NMR (CDCl3): d ˆ 14.04 (2C, CH3), 22.59, 26.97, 29.21,
31.77, 32.32 (10C, CH2), 39.84 (1C, CH2-NR'2), 54.87 (1C, CH), 62.88 (1C,
CH2-OR), 121.16, 122.52, 122.67, 122.81, 125.28, 125.69, 125.86, 125.93,
126.00, 126.11, 128.48, 129.11, 129.17, 131.14, 132.58, 133.73, 134.03, 134.33
3
CH2), 3.71 (brs, 1H; 1NH), 4.64 (t, J(H,H) ˆ 4.6 Hz, 2H; CH2-OR), 4.73
(t, 2H; CH2-NR'2), 5.20 (m, 1H; 1CH), 7.59 (m, 3H; 3CH anthraquinone),
7.82 (m, 1H; 1CH anthraquinone), 7.93 (m, 1H; 1-H anthraquinone), 8.00
(m, 2H; 2CH anthraquinone), 8.40 (d, 3J(H,H) ˆ 7.9 Hz, 2H; 2CH
perylene), 8.43 (d, 3J(H,H) ˆ 7.9 Hz, 2H; 2CH perylene), 8.53 (d,
3J(H,H) ˆ 7.9 Hz, 2H; 2CH perylene), 8.61 (brs, 2H; 2CH perylene);
UV/Vis (CHCl3): lmax (e) ˆ 262 (49620), 276 (34260), 286 (31430), 371
(7030), 434 (4210), 461 (15760), 493 (45220), 529 nm (75190); fluorescence
(CHCl3): lmax (Irel) ˆ 538 (1.00), 580 (0.57), 617 nm (0.14); fluorescence
quantum yield (lexc ˆ 491 nm, E491 nm ˆ 0.0345/1 cm, CHCl3, reference 1a
with F ˆ 1.00) ˆ 0.86; solid-state fluorescence: lmax ˆ 633 nm br; MS FAB
‡
‡
(3-NBA): m/z (%): 895 (1) [M ‡H], 894 (2) [M ], 893 (1), 628 (8), 627 (17)
‡
[M À C15H7NO3 À H2O], 626 (2), 625 (3), 550 (2), 419 (6), 418 (19), 417
‡
(36) [M À C15H7NO3 À C15H30 À H2O], 391 (7), 390 (10), 373 (10), 345 (5),
307 (19), 154 (100); elemental analysis calcd (%) for C56H51N3O8 (894.0): C
75.23, H 5.75, N 4.70; found: C 75.37, H 5.80, N 4.85.
Condensation of perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-car-
boxylic imides with aromatic amines; general procedure: N-(sec-Alkyl)-
perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carboxylic imide (2)
(0.35 mmol), the corresponding aminoaryl compound (0.42 mmol) zinc
acetate dihydrate (0.46 mmol) and imidazole (3.5 g) were heated at 1508C
for 2 h. The solution was cooled, but still warm a small amount of ethanol
was added, acidified with 2n HCl, stirred for 30 min, collected by vacuum
filtration stirred with boiling aqueous potassium carbonate solution (10%),
collected by vacuum filtration, washed with distilled water and dried in air
(1008C, 16 h).
ˆ
(30C, Ar), 154.51, 163.27 (5C, C O perylene and urethane); UV/Vis
(CHCl3): lmax (e) ˆ 261 (35050), 293 (10910), 371 (4120), 434 sh (5060), 459
(17710), 490 (49050), 527 nm (81970); fluorescence (CHCl3): lmax (Irel) ˆ
535 (1.00), 578 (0.52), 640 nm (0.13); fluorescence quantum yield (lexc
ˆ
490 nm, E490 nm ˆ 0.0334/1 cm, CHCl3, reference 1a with F ˆ 1.00) ˆ 0.54;
‡
‡
MS FAB (3-NBA): m/z (%): 787 (1) [M ‡H], 786 (2) [M ], 784 (3), 617
‡
‡
(4), 616 (7) [M À C11H7NO], 604 (14) [M À C13H26], 601 (11), 599 (100),
N-(1-Hexylheptyl)-N'-(1-anthraquinonyl)-perylene-3,4:9,10-tetracarboxy-
lic bisimide (9a): 1-Amino-anthraquinone (90 mg, 0.42 mmol), N-(1-
hexylheptyl)-perylene-3,4:9,10-tetracarboxylic-3,4-carboximide-9,10-anhy-
dride (2a, 200 mg, 0.35 mmol) and 1-aminoanthraquinone (90 mg,
0.42 mmol) were allowed to react according to the general procedure,
purified by two column separations (Al2O3 N I, chloroform and silica gel,
chloroform/acetone 15:1) and an extractice recrystallization from ethanol
to yield a red powder (100 mg, 37%). M.p. 340 3438C; Rf (silica gel,
CHCl3/acetone 15:1) ˆ 0.80; Rf (Al2O3 N I, CHCl3) ˆ 0.55; IR (KBr): nÄ
ˆ3080w, 2954m, 2927m, 2856m, 1720s, 1698s, 1662s, 1594s, 1580m,
1433m, 1405m, 1371m, 1344s, 1320m, 1279m, 1257m, 1203m, 1176m,
811m, 747m, 709m, 636 cmÀ1 m; 1H NMR (400 MHz, CDCl3, 258C, TMS):
d ˆ 0.84 (t, 6H; 2CH3), 1.31 (m, 16H; 8CH2), 1.88 (m, 2H; a-CH2), 2.27 (m,
‡
435 [M À C15H7NO À C13H26] (6), 419 (11), 418 (36), 417 (57), 391 (9), 390
(6), 373 (10), 345 (6); elemental analysis calcd (%) for C50H47N3O6 (785.9):
C 76.41, H 6.03, N 5.35; found: C 76.17, H 6.15, N 5.23.
N-(1-Hexylheptyl)-N'-(2-ethylcarbamyl-N-(2'-anthraquinonyl))-perylene-
3,4:9,10-tetracarboxylic bisimide (12a): Anthraquinone-2-isocyanate
(90 mg, 0.36 mmol), N-(1-hexylheptyl)-N'-(2-hydroxyethyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (8a, 140 mg, 0.23 mmol) and anhydrous
ligorine (5 mL) were heated under reflux under Ar for 5 h, cooled to room
temperature, collected by vacuum filtration (G4), dried (1308C, 16 h) and
purified by column separation (silica gel, chloroform/acetic acid 10:1) and
extractive recrystallization from chloroform to yield a bright red powder
(30 mg, 15%). M.p. 283 2858C; Rf (silica gel, CHCl3/acetic acid 10:1) ˆ
Chem. Eur. J. 2002, 8, No. 24
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0947-6539/02/0824-5639 $ 20.00+.50/0
5639

H. Langhals and S. Saulich
FULL PAPER
2H; a-CH2), 5.20 (m, 1H; 1CH), 7.68 (dt, 3J(H,H) ˆ 7.5 Hz, J(H,H) ˆ
1.4 Hz, 1H; 7-H anthraquinone), 7.74 (dd, 3J(H,H) ˆ 7.7 Hz, 4J(H,H) ˆ
1.3 Hz, 1H; 2-H anthraquinone), 7.76 (dt, 3J(H,H) ˆ 7.5 Hz, 4J(H,H) ˆ
1.3 Hz, 1H; 6-H anthraquinone), 8.00 (t, 3J(H,H) ˆ 7.8 Hz, 1H; 3-H
anthraquinone), 8.03 (dd, 3J(H,H) ˆ 7.8 Hz, 4J(H,H) ˆ 1.4 Hz, 1H; 8-H
anthraquinone), 8.29 (dd, 3J(H,H) ˆ 7.8 Hz, 4J(H,H) ˆ 1.4 Hz, 1H; 5-H
anthraquinone), 8.58 (dd, 3J(H,H) ˆ 7.9 Hz, 4J(H,H) ˆ 1.4 Hz, 1H; 4-H
anthraquinone), 8.67 (d, 3J(H,H) ˆ 7.6 Hz, 2H; 2CH perylene), 8.68 (d,
3J(H,H) ˆ 7.9 Hz, 4H; 4CH perylene), 8.74 (d, 3J(H,H) ˆ 8.0 Hz, 2H; 2CH
perylene); 13C NMR (CDCl3): d ˆ 14.03 (2C, CH3), 22.59, 26.96, 29.22,
31.77, 32.43 (10C, 10CH2), 54.85 (1C, CH), 123.07, 123.25, 123.51, 126.50,
127.01, 127.35, 128.99, 129.24, 129.61, 130.29, 131.80, 132.74, 134.03, 134.12,
134.41, 134.63, 135.37, 135.67, 135.84 (32C, CH perylene, CH anthraqui-
(CHCl3): lmax (Irel) ˆ 536 (1.00), 577 (0.57), 528 nm (0.17); fluorescence
quantum yield (lexc ˆ 490 nm, E490 nm ˆ 0.0311/1 cm, CHCl3, reference 1a
‡
with F ˆ 1.00) ˆ 0.42; MS (70 eV): m/z (%): 749 (57) [M ‡H], 748 (100)
‡
‡
[M ], 569 (6), 568 (22), 567 (60), 566 (100) [M À C13H26], 521 (8), 374 (9),
373 (36), 345 (11), 283 (6); elemental analysis calcd (%) for C51H44N2O4
(748.9): C 81.79, H 5.92, N 3.74; found: C 81.85, H 5.72, N 3.72.
N-(1-Hexylheptyl)-N'-(2-anthracenyl)-perylene-3,4:9,10-tetracarboxylic
bisimide (9d): 2-Amino-anthracene (80 mg, 0.41 mmol) and N-(1-hexyl-
heptyl)-perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carboximide
(2a, 200 mg, 0.35 mmol) were allowed to react according to the general
procedure and purified by two column separations (Al2O3 N I, chloroform
and silica gel, chloroform/acetone 15:1) and extractive recrystallizations
from chloroform and toluene to yield a red powder (50 mg, 19%). M.p.
>3508C; Rf (silica gel, CHCl3/acetone 15:1) ˆ 0.83; Rf (silica gel, CHCl3) ˆ
0.32; Rf (Al2O3 N I, CHCl3) ˆ 0.77; IR (KBr): nÄ ˆ2954m, 2927m, 2856m,
1698s, 1660s, 1594s, 1579m, 1459w, 1433w, 1405m, 1343s, 1254m, 1176m,
810m, 746 cmÀ1 m; 1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.83 (t,
6H; 2CH3), 1.28 (m, 16H; 8CH2), 1.87 (m, 2H; a-CH2), 2.25 (m, 2H; a-
CH2), 5.19 (m, 1H; 1CH), 6.07 (s, 1H; anthracene), 6.13 (s, 1H; 1CH
anthracene), 7.29 (dd, 3J(H,H) ˆ 7.7 Hz, 4J(H,H) ˆ 1.9 Hz, 1H; 3-H anthra-
cene), 7.33 (m, 2H; 2CH anthracene), 7.44 (m, 3H; 3CH anthracene), 7.62
ˆ
ˆ
none), 163.85 (4C, C O), 182.43, 182.60 (2C, C O anthraquinone); UV/
Vis (CHCl3): lmax (e) ˆ 259 sh (61380), 273 sh (22020), 326 sh (8520), 431 sh
(5270), 460 (19190), 491 (53120), 529 nm (87670); fluorescence (CHCl3):
lmax (Irel) ˆ 536 (1.00), 578 (0.53), 626 nm (0.12); fluorescence quantum
yield (lexc ˆ 490 nm, E490 nm ˆ 0.0311/1 cm, CHCl3, reference 1a with F ˆ
‡
‡
1.00) ˆ 0.97; MS (70 eV): m/z (%): 779 (12) [M ‡H], 778 (24) [M ], 761
‡
(5), 599 (6), 598 (27), 597 (82), 596 (100) [M À C13H26], 569 (5), 568 (20),
567 (41), 540 (12), 523 (9), 522 (8); elemental analysis calcd (%) for
C51H42N2O6: 778.3043; found: 778.3077 (MS); elemental analysis calcd (%)
for C51H42N2O6 (778.2): C 78.64, H 5.44, N 3.60; found: C 78.35, H 5.50, N
3.53.
3
(d, J(H,H) ˆ 7.6 Hz, 1H; 4-H anthracene), 8.74 (m, 8H; 8CH perylene);
13C NMR (CDCl3): d ˆ 14.02 (2C, CH3), 22.57, 26.94, 29.20, 31.75, 32.40
(10C, 10CH2), 118.07, 123.10, 128.03, 131.99, 145.44; UV/Vis (CHCl3): lmax
(e) ˆ 258 (255900), 260 (245650), 343 (8560), 358 (10470), 378 (7800), 460
(19880), 491 (53650), 528 nm (87050); fluorescence (CHCl3): lmax (Irel) ˆ
N-(1-Hexylheptyl)-N'-(2-anthraquinonyl)-perylene-3,4:9,10-tetracarboxy-
lic bisimide (9b): 2-Amino-anthraquinone (90 mg, 0.42 mmol) and N-(1-
hexylheptyl)-perylene-3,4:9,10-tetracarboxylic-3,4-carboximide-9,10-anhy-
dride (2a, 200 mg, 0.35 mmol) were allowed to react according to the
general procedure and purified by a column separation (Al2O3 N I,
chloroform) and an extractive recrystallization from ethanol to yield a red
solid (900 mg, 33%). M.p. >3508C; Rf (silica gel, CHCl3/acetone 15:1) ˆ
0.79; Rf (Al2O3 N I, CHCl3) ˆ 0.64; IR (KBr): nÄ ˆ3070w, 2955m, 2927m,
2856m, 1698s, 1676s, 1660s, 1594s, 1579m, 1405m, 1342s, 1325w, 1286m,
1253m, 1175m, 811m, 746m, 712 cmÀ1 m; 1H NMR (400 MHz, CDCl3,
258C, TMS): d ˆ 0.83 (t, 6H; 2CH3), 1.29 (m, 16H; 8CH2), 1.88 (m, 2H; a-
CH2), 2.27 (m, 2H; a-CH2), 5.20 (m, 1H; 1CH), 7.83 (m, 3H; 3CH
anthraquinone), 8.37 (m, 3H; 3CH anthraquinone), 8.54 (d, 3J(H,H) ˆ
8.1 Hz, 1H; 1CH anthraquinone), 8.54 (d, 3J(H,H) ˆ 8.1 Hz, 6H; 6CH
perylene), 8.78 (d, 3J(H,H) ˆ 8.0 Hz, 2H; 2CH perylene); UV/Vis (CHCl3):
lmax (e) ˆ 256 (80850), 276 sh (24370), 323 (9790), 436 sh (5590), 461
(18270), 491 (49560), 528 nm (82150); fluorescence (CHCl3): lmax (Irel) ˆ
536 (1.00), 578 (0.57), 631 nm, (0.19); fluorescence quantum yield (lexc
ˆ
490 nm, E490 nm ˆ 0.0331/1 cm, CHCl3, reference 1a with F ˆ 1.00) ˆ 0.04;
‡
‡
MS (70 eV): m/z (%): 749 (39) [M ‡H], 748 (68) [M ], 569 (10), 568 (34),
‡
567 (83), 566 (100) [M À C13H26], 565 (9), 522 (7), 521 (16), 374 (11), 373
‡
(41), 346 (7), 345 (21), 328 (5), 284 (6), 283 (10), 182 (5) [C13H26 ];
elemental analysis calcd (%) for C51H44N2O4 (748.9): C 81.79, H 5.92, N
3.74; found: C 81.37, H 5.87, N 3.74.
N-(Hexylheptyl)-N'-(1-naphthyl)-perylene-3,4:9,10-tetracarboxylic bisim-
ide (9e): N-(1-Hexylheptyl)-perylene-3,4:9,10-tetracarbons‰ure-3,4-an-
hydride-9,10-carboximide (100 mg, 0.17 mmol), 1-aminonaphthalene
(30 mg, 0.30 mmol), zinc acetate dihydrate (40 mg, 0.18 mmol) and
Imidazol (3.5 g) were allowed to react according to the general procedure
and purified by two column separations (Al2O3 N I, chloroform and silica
gel, chloroform for an orange forerun and chloroform/acetone 15:1 for the
broad orange main fraction) to yield a red powder (100 mg, 82%). M.p.
>3508C; Rf (silica gel/CHCl3/acetone 15:1) ˆ 0.65; Rf (Al2O3 N I,
CHCl3) ˆ 0.62; IR (KBr): nÄ ˆ3070w, 2954m, 2927m, 2856m, 1710s,
1698s, 1660s, 1594s, 1579m, 1432w, 1405m, 1393w, 1341s, 1253s, 1176w,
811m, 790m, 770w, 746m, 636 cmÀ1 m; UV/Vis (CHCl3): lmax (e) ˆ 261
(36840), 281 (11670), 291 (9810), 369 (4240), 433 sh (5400), 459 (18950),
490 (52370), 527 nm (87190); fluorescence (CHCl3): lmax (Irel) ˆ 536 (1.00),
536 (1.00), 578 (0.54), 628 nm (0.13); fluorescence quantum yield (lexc
ˆ
488 nm, E488 nm ˆ 0.0374/1 cm, CHCl3, reference 1a with F ˆ 1.00) ˆ 0.01;
‡
‡
MS (70 eV): m/z (%): 779 (7) [M ‡H], 778 (13) [M ], 599 (5), 598 (23), 597
‡
(67), 596 (100) [M À C13H26], 595 (11); elemental analysis calcd (%) for
C51H42N2O6: 778.3043; found: 778.3106 (MS); elemental analysis calcd (%)
for C51H42N2O6 (778.2): C 78.64, H 5.44, N 3.60; found: C 77.94, H 5.69, N
3.66.
‡
578 (0.53), 627 nm (0.12); MS (70 eV): m/z (%): 699 (11) [M ‡H], 698 (20)
‡
‡
[M ], 681 (7), 518 (24), 517 (72), 516 (100) [M À C13H26,], 515 (8), 500 (6),
499 (12), 471 (11), 374 (10), 373 (37), 182 (2); elemental analysis calcd (%)
for C47H42N2O4 (698.9): C 80.78, H 6.06, N 4.01; found: C 81.00, H 6.12, N
4.20.
N-(1-Hexylheptyl)-N'-(1-anthracenyl)-perylene-3,4:9,10-tetracarboxylic
bisimide (9c): 1-Aminoanthracene (80 mg, 0.41 mmol) and N-(1-hexylhep-
tyl)-perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carboximide (2a,
200 mg, 0.35 mmol) were allowed to react according to the general
procedure and purified by two column separations (Al2O3 N I, chloroform
and silica gel, chloroform/acetone 15:1; orange forerun and broad red main
fraction) and an extractive recrystallization from toluene. Yield 110 mg
(42%) of 9c, orange powder, m.p. ?3508C; Rf (silica gel, CHCl3/acetone
15:1) ˆ 0.70; Rf (silica gel, CHCl3) ˆ 0.23; Rf (Al2O3 N I), CHCl3) ˆ 0.63; IR
(KBr): nÄ ˆ3050w, 2954m, 2928m, 2856m, 1698s, 1660s, 1594s, 1579m,
1430w, 1405m, 1342s, 1253m, 1176m, 811m, 747m, 730w, 637 cmÀ1 w;
1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.84 (t, 6H; 2CH3), 1.29 (m,
16H; 8CH2), 1.89 (m, 2H; a-CH2), 2.28 (m, 2H; a-CH2), 5.21 (m, 1H;
1CH), 7.40 (dd, 1H; 1CH anthracene), 7.32 (m, 1H; 2CH anthracene), 7.45
(d, 2H; 2CH anthracene), 7.47 (t, 3J(H,H) ˆ 8.3 Hz, 1H; 1CH anthracene),
N-(Hexylheptyl)-N'-(3-pyrenyl)-perylene-3,4:9,10-tetracarboxylic bisimide
(9 f): 3-Amino-pyrene (90 mg, 0.42 mmol), N-(1-hexylheptyl)-perylene-
3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carboximide (2a, 200 mg,
0.35 mmol), zinc acetate dihydrate (100 mg, 0.46 mmol) and imidazole
(3.5 g) were allowed to react according to the general procedure and
purified by column separation (Al2O3 N I, chloroform) to yield a red
powder (220 mg, 68%). M.p. >3508C; Rf (silica gel, CHCl3/acetone
15:1) ˆ 0.85; Rf (Al2O3 N I, CHCl3) ˆ 0.76; IR (KBr): nÄ ˆ3050w, 2954m,
2926m, 2856m, 1720w, 1696s, 1660s, 1616w, 1594s, 1579m, 1437w, 1405m,
1343s, 1254m, 1175w, 844w, 811m, 749 cmÀ1 m; 1H NMR (400 MHz,
CDCl3, 258C, TMS): d ˆ 0.84 (t, 6H; 2CH3), 1.32 (m, 16H; 8CH2), 1.87 (m,
2H; a-CH2), 2.24 (m, 2H; a-CH2), 5.21 (m, 1H; CH), 7.84 (d, 3J(H,H) ˆ
9.2 Hz, 1H; 10-H pyrene), 7.93 (t, 3J(H,H) ˆ 7.7 Hz, 1H; 7-H pyrene), 7.98
(d, 3J(H,H) ˆ 9.3 Hz, 1H; 9-H pyrene), 8.02 (d, 3J(H,H) ˆ 8.1 Hz, 1H; 2-H
pyrene), 8.05 (s, 4-H pyrene, 2H; 5-H pyrene), 8.06 (d, 3J(H,H) ˆ 8.1 Hz,
1H; 8-H pyrene), 8.13 (d, 3J(H,H) ˆ 8.1 Hz, 1H; 6-H pyrene), 8.32 (d,
3J(H,H) ˆ 8.1 Hz, 1H; 3-H pyrene), 8.54 (d, 3J(H,H) ˆ 8.3 Hz, 2H; 2CH
perylene), 8.58 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene). 8.63 (brs, 2H;
3
7.55 (d, J(H,H) ˆ 7.2 Hz, 1H; 1CH anthracene), 8.72 8.76 (m, 8H; 8CH
perylene), 8.81 (s, 1H; 1CH anthracene), 8.84 (s, 1H; 1CH anthracene);
13C NMR (CDCl3): d ˆ 14.01 (2C, CH3), 22.56, 26.91, 29.18, 31.74, 32.37
(10C, 10CH2), 54.84 (1C, CH), 122.85 123.03, 123.22, 123.53, 124.22,
126.85, 128.06, 128.41, 129.60, 132.07, 132.36, 133.80, 135.46, 135.60, 137.28,
ˆ
137.57, 139.43 (34C, CH perylene, CH anthracene), 163.05 (4C, C O); UV/
Vis (CHCl3): lmax (e) ˆ 258 (97790), 345 (4930), 363 (6770), 384 (5610), 435
3
sh (2970), 461 (11390), 492 (30440), 529 nm (49700); fluorescence
2CH perylene), 8.75 (d, J(H,H) ˆ 8.0 Hz, 2H; 2CH perylene); 13C NMR
5640
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0947-6539/02/0824-5640 $ 20.00+.50/0
Chem. Eur. J. 2002, 8, No. 24

Bichromophoric Perylene Derivatives
5630 5643
(CDCl3): d ˆ 14.03 (2C, CH3), 22.58, 26.98, 29.22, 31.77, 32.40 (10C,
10CH2), 54.82 (1C, CH), 121.16, 123.05, 123.16, 123.30, 124.48, 125.33,
125.45, 125.53, 125.80, 126.12, 126.22, 126.51, 126.64, 127.11, 127.97, 128.09,
128.94, 129.06, 129.37, 130.06, 130.65, 130.87, 131.84, 131.99, 134.11 (36C,
(20), 345 (4); elemental analysis calcd (%) for C50H42N2O5 (750.9): C 79.98,
H 5.64, N 3.73; found: C 77.58, H 5.50, N 3.64; analysis calcd for
C50H42N2O5: 750.3093; found: 750.3094 (HRMS).
N-(1-Hexylheptyl)-N'-(3-fluorene-9-onyl)-perylene-3,4:9,10-tetracarboxy-
lic bisimide (9i): 3-Amino-fluorene-9-one (80 mg, 0.41 mmol), N-(1-
hexylheptyl)-perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carbox-
imide (2a, 200 mg, 0.35 mmol), zinc acetate dihydrate (100 mg, 0.46 mmol)
and imidazole (3.5 g) were allowed to react according to the general
procedure and purified by column separation (Al2O3 N I, chloroform) to
yield a red powder (150 mg, 57%). M.p. >3508C; Rf (silica gel, CHCl3/
acetone 15:1) ˆ 0.48; Rf (Al2O3 N I, CHCl3) ˆ 0.50; IR (KBr): nÄ ˆ3080w,
2954m, 2927m, 2856m, 1713s, 1700s, 1660s, 1614w, 1594s, 1579m, 1448w,
1432w, 1405m, 1342s, 1254m, 1176w, 810m, 746 cmÀ1 m; 1H NMR
(400 MHz, CDCl3, 258C, TMS): d ˆ 0.83 (t, 6H; 2CH3), 1.31 (m, 16H;
8CH2), 1.90 (m, 2H; a-CH2), 2.27 (m, 2H; a-CH2), 5.12 (m, 1H; 1CH), 7.30
(dd, 3J(H,H) ˆ 7.6 Hz, 4J(H,H) ˆ 1.6 Hz, 1H; 2-H fluorenone), 7.33 (dt,
3J(H,H) ˆ 7.9 Hz, 4J(H,H) ˆ 1.6 Hz, 1H; 7-H fluorenone), 7.45 (d,
ˆ
CH perylene, CH pyrene), 163.97 (4C, C O); UV/Vis (CHCl3): lmax (e) ˆ
261 (52560), 277 (52530), 312 (16610), 326 (30800), 342 (43170), 366
(5650), 435 sh (6690), 460 (21180), 491 (56650), 528 nm (92840);
fluorescence (CHCl3): lmax (Irel) ˆ 534 (1.00), 579 (0.60), 635 nm (0.19);
fluorescence quantum yield (lexc ˆ 491 nm, E491 nm ˆ 0.0296/1 cm, CHCl3,
reference 1a with F ˆ 1.00) ˆ 0.01; MS (70 eV): m/z (%): 773 (41), 772 (70)
‡
‡
[M ], 593 (8), 592 (33), 591 (86), 590 (100) [M À C13H26,], 545 (14), 374
(17), 373 (64), 346 (12), 345 (24), 328 (8), 296 (9), 202 (12); elemental
analysis calcd (%) for C53H44N2O4 (772.9): C 82.36, H 5.74, N 3.62; found: C
82.19, H 5.75, N 3.88.
N-(1-Hexylheptyl)-N'-(1-fluorene-9-onyl)-perylene-3,4:9,10-tetracarboxy-
lic bisimide (9g): 1-Amino-fluorene-9-one (80 mg, 0.41 mmol), N-(1-
hexylheptyl)-perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carbox-
imide (2a, 200 mg, 0.35 mmol), zinc acetate dihydrate (100 mg, 0.46 mmol)
and imidazole (3.5 g) were allowed to react according to the general
procedure and purified by column separation (Al2O3 N I, chloroform) to
yield a red powder (150 mg, 57%). M.p. 327 3298C; Rf (silica gel, CHCl3/
acetone 15:1) ˆ 0.67; Rf (Al2O3 N I, CHCl3) ˆ 0.61; IR (KBr): nÄ ˆ3080w,
2954m, 2927m, 2856m, 1713s, 1698s, 1658s, 1610m, 1594s, 1579m, 1452w,
1434w, 1405m, 1343s, 1255m, 1200w, 1176w, 811m, 755m, 747 cmÀ1 m;
1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.82 (t, 6H; 2CH3), 1.27 (m,
16H; 8CH2), 1.86 (m, 2H; a-CH2), 2.24 (m, 2H; a-CH2), 5.18 (m, 1H;
3
3J(H,H) ˆ 7.3 Hz, 1H; 5-H fluorenone), 7.48 (t, J(H,H) ˆ 7.8 Hz, 1H; 6-H
fluorenone), 7.57 (d, 4J(H,H) ˆ 1.7 Hz, 1H; 4-H fluorenone), 7.68 (d,
3J(H,H) ˆ 7.4 Hz, 1H; 8-H fluorenone), 7.85 (d, 3J(H,H) ˆ 7.7 Hz, 1H; 1-H
fluorenone), 8.60 (d, 3J(H,H) ˆ 8.3 Hz, 2H; 2CH perylene), 8.66 (brs, 2H;
2CH perylene), 8.72 (d, 3J(H,H) ˆ 8.0 Hz, 2H; 2CH perylene); COSY
NMR: cross-peaks at d ˆ (7.30, 7.57, 7.85), (7.33, 7.45, 7.48, 7.68); 13C NMR
(CDCl3): d ˆ 14.01 (2C, CH3), 22.56, 26.97, 29.19, 31.74, 32.37 (10C,
10CH2), 54.91 (1C, CH), 120.73, 121.37, 122.86, 123.02, 123.39, 124.44,
125.08, 126.28, 126.62, 129.43, 129.49, 129.55, 129.76, 131.88, 134.00, 134.25,
134.30, 134.78, 135.34, 140.87, 143.65, 145.86 (32C, CH perylene, CH
3
3
1CH), 7.23 (t, J(H,H) ˆ 7.3 Hz, 1H; 7-H fluorenone), 7.27 (dd, J(H,H) ˆ
7.3 Hz, 4J(H,H) ˆ 1.3 Hz, 1H; 2-H fluorenone), 7.47 (t, 3J(H,H) ˆ 7.5 Hz,
1H; 6-H fluorenone), 7.48 (d, 3J(H,H) ˆ 7.5 Hz, 1H; 8-H fluorenone), 7.56
(d, 3J(H,H) ˆ 7.3 Hz, 1H; 5-H fluorenone), 7.64 (dd, 3J(H,H) ˆ 7.6 Hz,
4J(H,H) ˆ 1.4 Hz, 1H; 4-H fluorenone), 7.67 (t, 3J(H,H) ˆ 7.5 Hz, 1H; 3-H
fluorenone), 8.59 (d, 3J ˆ 8.1 Hz, 4H; 4CH perylene), 8.65 (brs, 2H; 2CH
perylene), 8.68 (d, 3J(H,H) ˆ 8.0 Hz, 2H; 2CH perylene); COSY NMR
(CDCl3): cross-peaks at d ˆ (7.23, 7.47, 7.48, 7.56), (7.27, 7.63, 7.67); 13C NMR
(CDCl3): d ˆ 14.01 (2C, CH3), 22.56, 26.93, 29.20, 31.74, 32.38 (10C,
10CH2), 54.78 (1C, CH), 120.52, 120.97, 122.99, 123.22, 123.28, 124.39,
129.38, 130.23, 131.74, 134.83, 135.10, 135.57, 143.77, 146.00 (32C, CH
ˆ
ˆ
fluorenone), 163.24 (4C, C O), 192.74 (1C, C O fluorenone); UV
(CHCl3): lmax (e) ˆ 252 (89280), 261 (127320), 369 (4580), 434 sh (5560),
460 (19280), 491 (53420), 528 nm (89190); fluorescence (CHCl3): lmax
(Irel) ˆ 537 (1.00), 581 (0.53), 630 nm (0.13); fluorescence quantum yield
(lexc ˆ 491 nm, E491 nm ˆ 0.0266/1 cm, CHCl3, reference 1a with F ˆ 1.00) ˆ
‡
0.94; MS (70 eV): m/z (%): 751 (8), 750 (14) [M ], 571 (6), 570 (30), 569
‡
(78), 568 (100) [M À C13H26], 567 (28), 523 (9), 442 (9), 373 (15), 182 (6)
‡
[C13H26 ]; elemental analysis calcd (%) for C50H42N2O5 (750.9): C 79.98, H
5.64, N 3.73; found: C 80.26, H 5.97, N 3.77.
N-(1-Hexylheptyl)-N'-(4-fluorene-9-onyl)-perylene-3,4:9,10-tetracarboxy-
lic bisimide (9j): 4-Amino-fluorene-9-one (80 mg, 0.41 mmol), N-(1-
hexylheptyl)-perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carbox-
imide (2a, 200 mg, 0.35 mmol), zinc acetate dihydrate (100 mg, 0.46 mmol)
and imidazole (3.5 g) were allowed to react according to the general
procedure and purified by column separation (Al2O3 N I, chloroform) to
yield a red powder (120 mg, 46%). M.p. >3508C; Rf (silica gel, CHCl3/
acetone 15:1) ˆ 0.55; Rf (Al2O3 N I, CHCl3) ˆ 0.56; IR (KBr): nÄ ˆ3080w,
2954m, 2927m, 2855m, 1713s, 1698s, 1660s, 1611w, 1594s, 1579m, 1468w,
1432w, 1405m, 1342s, 1302w, 1253m, 1176w, 811m, 747m, 734 cmÀ1 m;
1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.83 (t, 6H; 2CH3), 1.31 (m,
16H; 8CH2), 1.88 (m, 2H; a-CH2), 2.25 (m, 2H; a-CH2), 5.17 (m, 1H;
ˆ
ˆ
perylene, CH fluorenone), 163.18 (4C, C O), 191.55 (1C, C O fluore-
none); UV (CHCl3): lmax (e) ˆ 252 (77490), 261 (94380), 369 (4560), 432 sh
(5490), 459 (19320), 490 (53700), 527 nm (89850); fluorescence (CHCl3):
lmax (Irel.) ˆ 535 (1.00), 578 (0.52), 626 nm (0.12); fluorescence quantum
yield (lexc ˆ 490 nm, E490 nm ˆ 0.0368/1 cm, CHCl3, reference 1a with F ˆ
‡
1.00) ˆ 1.01; MS (70 eV): m/z (%): 752 (18), 751 (33) [M ], 733 (7), 571 (8),
‡
570 (35), 569 (100) [M À C13H26], 568 (84), 542 (7), 541 (35), 540 (77), 539
(14), 513 (5), 512 (17), 511 (12), 496 (8), 495 (11); elemental analysis calcd
(%) for C50H42N2O5 (750.9): C 79.98, H 5.64, N 3.73; found: C 80.00, H 5.75,
N 3.78.
N-(1-Hexylheptyl)-N'-(2-fluorene-9-onyl)-perylene-3,4:9,10-tetracarboxy-
lic bisimide (9h): 2-Amino-fluorene-9-one (80 mg, 0.41 mmol), N-(1-
hexylheptyl)-perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-carbox-
imide (2a, 200 mg, 0.35 mmol), zinc acetate dihydrate (100 mg, 0.46 mmol)
and imidazole (3.5 g) were allowed to react according to the general
procedure and purified by column separation (Al2O3 N I, chloroform) to
yield a violet powder (50 mg, 19%). M.p. >3508C; Rf (silica gel, CHCl3/
acetone 15:1) ˆ 0.85; Rf (Al2O3 N I, CHCl3) ˆ 0.88; IR (KBr): nÄ ˆ3070w,
2954m, 2927m, 2856m, 1698 (brs), 1658s, 1616w, 1594s, 1579m, 1457m,
1430w, 1405m, 1342s, 1254m, 1191w, 1176m, 1100w, 811s, 746m, 738 cmÀ1
3
3
1CH), 7.01 (d, J(H,H) ˆ 7.5 Hz, 1H; 5-H fluorenone), 7.16 (dt, J(H,H) ˆ
4
3
7.6 Hz, J(H,H) ˆ 1.3 Hz, 1H; 7-H fluorenone), 7.22 (dt, J(H,H) ˆ 7.4 Hz,
4J(H,H) ˆ 1.1 Hz, 1H; 6-H fluorenone), 7.43 (dd, 3J(H,H) ˆ 7.9 Hz,
4J(H,H) ˆ 1.1 Hz, 1H; 3-H fluorenone), 7.52 (t, 3J(H,H) ˆ 7.7 Hz, 1H;
2-H fluorenone), 7.67 (dd, 3J(H,H) ˆ 7.3 Hz, 4J(H,H) ˆ 1.3 Hz, 1H; 8-H
fluorenone), 7.84 (dd, 3J(H,H) ˆ 7.3 Hz, 4J(H,H) ˆ 1.4 Hz, 1H; 1-H fluo-
renone), 8.73 (d, 3J(H,H) ˆ 8.0 Hz, 6H; 6CH perylene), 8.80 (d, 3J(H,H) ˆ
8.1 Hz, 2H; 2CH perylene); COSY NMR: cross-peaks at d ˆ (7.01, 7.22),
(7.16, 7.22), (7.43, 7.52), (7.52, 7.84); 13C NMR (CDCl3): d ˆ 14.02 (2C, CH3),
22.58, 26.95, 29.20, 31.75, 32.39 (10C, 10CH2), 54.91 (1C, CH), 121.73,
122.72, 123.19, 123.63, 124.62, 129.47, 130.15, 130.28, 132.37, 135.79, 135.87,
136.10, 141.45, 142.39 (32C, CH perylene, CH fluorenone), 163.06 (4C,
1
w; H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.83 (t, 6H; 2CH3), 1.29
(m, 16H; 8CH2), 1.88 (m, 2H; a-CH2), 2.27 (m, 2H; a-CH2), 5.19 (m, 1H;
3
3
1CH), 7.36 (t, J(H,H) ˆ 7.4 Hz, 1H; 7-H fluorenone), 7.49 (dd, J(H,H) ˆ
7.6 Hz, 4J(H,H) ˆ 1.8 Hz, 1H; 5-H fluorenone), 7.55 (t, 3J(H,H) ˆ 7.5 Hz,
1H; 6-H fluorenone), 7.62 (d, 3J(H,H) ˆ 7.5 Hz, 1H; 8-H fluorenone), 7.64
ˆ
ˆ
C O), 192.60 (1C, C O fluorenone); UV (CHCl3): lmax (e) ˆ 251 (79330),
259 (85660), 370 (4780), 435 sh (5520), 460 (18750), 491 (51570), 528 nm
(85900); fluorescence (CHCl3): lmax (Irel) ˆ 536 (1.00), 581 (0.54), 529 nm
(0.13); fluorescence quantum yield (lexc ˆ 491 nm, E491 nm ˆ 0.0311/1 cm,
CHCl3, reference 1a with F ˆ 1.00) ˆ 0.98; MS (70 eV): m/z (%): 751 (19),
4
3
(d, J(H,H) ˆ 1.9 Hz, 1H; 1H; fluorenone), 7.72 (d, J(H,H) ˆ 7.6 Hz, 1H;
3-H fluorenone), 7.73 (d, 3J(H,H) ˆ 7.6 Hz, 1H; 4-H fluorenone), 8.71 (d,
3J(H,H) ˆ 7.9 Hz, 6H; 6CH perylene), 8.77 (d, 3J(H,H) ˆ 8.0 Hz, 2H; 2CH
perylene); UV (CHCl3): lmax (e) ˆ 252 88310), 261 (122500), 368 (5080),
433 sh (6060), 459 (19990), 490 (54520), 527 nm (90640); fluorescence
(CHCl3): lmax (Irel) ˆ 536 (1.00), 579 (0.52), 626 nm (0.12); fluorescence
quantum yield (lexc ˆ 490 nm, E490 nm ˆ 0.0311/1 cm, CHCl3, reference 1a
‡
‡
750 (34) [M ], 733 (7), 571 (7), 570 (28), 569 (77), 568 (100) [M À C13H26],
552 (10), 551 (20), 523 (14), 373 (11); elemental analysis calcd (%) for
C50H42N2O5 (750.9): C 79.98, H 5.64, N 3.73; found: C 80.49, H 5.74, N 3.75;
analysis calcd for C50H42N2O5: 750.3094; found: 750.3042 (HRMS).
‡
with F ˆ 1.00) ˆ 1.01; MS (70 eV): m/z (%): 751 (11), 750 (20) [M ], 733
N-(1-Hexylheptyl)-N'-(3-methylpyrenyl)-perylene-3,4:9,10-tetracarboxylic
bisimide (10b): 3-Ainomethylpyrene hydrochloride (110 mg, 0.41 mmol),
‡
(5), 570 (24), 569 (72), 568 (100) [M À C13H26], 567 (9), 523 (4), 374 (5), 373
Chem. Eur. J. 2002, 8, No. 24
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0947-6539/02/0824-5641 $ 20.00+.50/0
5641

H. Langhals and S. Saulich
FULL PAPER
N-(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylic-3,4-anhydride-9,10-
carboximide (2a, 200 mg, 0.35 mmol) and imidazole (3.5 g) were allowed to
react according to the general procedure and purified by column separation
(Al2O3 N I, chloroform) to yield light red powder (200 mg, 73%). M.p.
>3508C; Rf (silica gel, CHCl3/acetone 15:1) ˆ 0.80; Rf (Al2O3 N I,
CHCl3) ˆ 0.71; IR (KBr): nÄ ˆ3050w, 2954m, 2927m, 2856m, 1695s,
1658s, 1594s, 1579m, 1437w, 1404m, 1355m, 1338s, 1253m, 1173w, 847w,
810m, 750 cmÀ1 m; 1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.82 (t,
6H; 2CH3), 1.27 (m, 16H; 8CH2), 1.88 (m, 2H; a-CH2), 2.26 (m, 2H; a-
CH2), 5.19 (m, 1H; CH), 6.13 (s, 2H; 1CH2), 7.91 (d, 3J(H,H) ˆ 8.9 Hz, 1H;
10-H pyrene), 7.94 (t, 3J(H,H) ˆ 7.4 Hz, 1H; 7-H pyrene), 7.95 (d,
3J(H,H) ˆ 9.0 Hz, 1H; 9-H pyrene), 8.03 (d, 3J(H,H) ˆ 8.2 Hz, 1H; 4-H
pyrene), 8.06 (d, 3J(H,H) ˆ 7.9 Hz, 1H; 5-H pyrene), 8.09 (d, 3J(H,H) ˆ
(7640), 370 (5060), 434 sh (5930), 459 (19580), 490 (53100), 527 nm
(87580); fluorescence (CHCl3): lmax (Irel) ˆ 537 (1.00), 579 (0.54), 629 nm
‡
‡
(0.13); MS (70 eV): m/z (%): 794 (19) [M ‡H], 793 (34) [M ], 776 (8), 613
‡
‡
(17), 612 (39), 611 (34) [M À C13H26], 406 (3), 405 (3), 391 (4), 390 [M
À
‡
‡
C13H26 À C14H7NO2] (5), 377 (4), 376 (7), 221 (50) [M À C14H7NO2 ], 208
(16), 207 (100); elemental analysis calcd (%) for C51H43N3O8 (793.9): C
77.16, H 5.46, N 5.29; found: C 77.01, H 5.49, N 5.31.
N-(1-Hexylheptyl)-N'-(aminocarbamyl-2'-fluorene-9-onyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (11b): N-(1-Hexylheptyl)-N'-(amino)-
perylene-3,4:9,10-tetracarboxylic bisimide (100 mg, 0.17 mmol) and fluo-
rene-9-one-2-isocyanate (120 mg, 0.54 mmol) in anhydrous toluene
(10 mL) were stirred under Ar at room temperature for 24 h, evaporated
in vacuo (12 mbar) and purified by column separation (silica gel, chloro-
form/acetone 15:1 for a light red forerun and chloroform/ethanol 20:1 for
the broad red main fraction) to yield a violet solid (110 mg, 80%). M.p.
296 2998C decomp; Rf (silica gel, CHCl3/acetone 15:1) ˆ 0.02; Rf (silica
gel, CHCl3/ethanol 20:1) ˆ 0.57; IR (KBr): nÄ ˆ3380w (NH), 3070w,
2927m, 2856m, 1730w, 1698s, 1660m, 1595s, 1579w, 1549w, 1493w, 1458m,
1430w, 1404w, 1346m, 1301m, 1253m, 1177m, 1109w, 810m, 765w,
738 cmÀ1 m; UV/Vis (CHCl3): lmax (e) ˆ 262 (75190), 272 (80030), 315 sh
(16770), 331 sh (11120), 436 sh (5110), 461 (13070), 492 (33390), 528 nm
(54510); fluorescence (CHCl3): lmax (Irel) ˆ 536 (1.00), 577 (0.63), 528 nm
3
7.7 Hz, 1H; 6-H pyrene), 8.14 (d, J(H,H) ˆ 7.8 Hz, 1H; 8-H pyrene), 8.17
(d, 1H; 3J(H,H) ˆ 9.3 Hz, 3-H pyrene), 8.50 (d, J(H,H) ˆ 8.2 Hz, 2H; 2CH
perylene), 8.52 (d, 3J(H,H) ˆ 9.0 Hz, 2H; 2CH perylene). 8.64 (d,
3J(H,H) ˆ 8.1 Hz, 4H; 4CH perylene), 8.66 (d, 3J(H,H) ˆ 9.6 Hz, 2H;
2-H pyrene); COSY NMR: cross-peaks at d ˆ (7.91,7.93), (7.94, 8.06, 8.09),
(8.03, 8.06), (8.17, 8.66); 13C NMR (CDCl3): d ˆ 13.97 (2C, CH3), 22.54,
26.93, 29.18, 31.73, 32.38 (10C, CH2), 41.49 (1C, CH2), 54.80 (1C, CH),
122.89, 123.03, 123.12, 124.69, 124.84, 125.05, 125.13, 125.83, 126.08, 126.27,
126.42, 127.22, 127.26, 127.81, 128.86, 129.45, 130.16, 130.69, 130.76, 131.22,
131.70, 132.08, 132.99, 134.19, 134.86, 139.30 (36C, CH perylene, CH
‡
‡
(0.18); MS FAB (3-NBA): m/z (%): 809 (1) [M ], 589 (6), 588 (13) [M
À
ˆ
pyrene), 162.65, 163.67 (4C, C O); UV/Vis (CHCl3): lmax (e) ˆ 261
‡
C14H7O2N], 587 (3), 407 (3), 406 (7) [M À C13H26 À C14H7O2N], 405 (4),
(45250), 278 (46850), 302 sh (8070), 315 (15790), 328 (32510), 344
(46060), 370 (4320), 434 sh (5160), 460 (19030), 491 (52840), 528 nm
(87020); fluorescence (CHCl3): lmax (Irel) ˆ 534 (1.0), 571 nm (0.6); MS
‡
392 (3), 391 (7) [M À C13H26 À C14H7O2N-NH], 390 (4), 376 (2), 362 (2),
361 (2); elemental analysis calcd (%) for C51H44N4O6 (808.9): C 75.72, H
5.48, N 6.93; found: C 74.45, H 5.15, N 6.59.
‡
‡
‡
(70 eV): m/z (%): 788 (4) [M ‡H], 787 (70) [M ], 605 (6) [M À C13H26],
Coupling of two chromophores by methylene spacers; general procedure:
N-(sec-Alkyl)-perylene-3,4:9,10-tetracarboxylic bisimide, the correspond-
ing alkyl bromide and potassium carbonate in anhydrous DMF were stirred
under Ar at 1008C for 24 h. 10% KOH was added and the mixture was
stirred at room temperature for 1 h, acidified with conc. HCl and stirred for
further 30 min. The precipitate was collected by vacuum filtration, dried at
1308C for 16 h and purified by column separation.
‡
604 (6), 416 (4), 391 (5), 390 (8) [M À C13H26 À C17H11], 217 (17), 216 (100),
215 (73), 182 (18); elemental analysis calcd (%) for C54H46N2O4 (787.0): C
82.42, H 5.89, N 3.56; found: C 82.99, H 5.91, N 3.73.
Coupling of chromophores by the formation of carboxylic amides; general
procedure: N-(sec-Alkyl)-N'-(amino)-perylene-3,4:9,10-tetracarboxylic bi-
simide (0.26 mmol) and a carboxylic chloride (0.52 mmol) in anhydrous
toluene (20 mL) were stirred under Ar at room temperature for 20 h. The
reaction product was collected by vacuum filtration (D4) and dried at
1308C for 16 h.
N2,N2'-Bis-(1-hexylheptyl)-N1,N1'-(1,2-ethandiyl)-bis-perylene-3,4:9,10-
tetracarboxylic bisimide: N-(1-Hexylheptyl)-perylene-3,4:9,10-tetracar-
boxylic bisimide (200 mg, 0.35 mmol), dibromomethane (0.70 mL,
10 mmol) and potassium carbonate (1.3 g, 9.4 mmol) in anhydrous DMF
(20 mL) and 10% KOH (5 mL) were allowed to react according to the
general procedure and purified by two column separations (silica gel,
chloroform/n-butanol 40:1 and chloroform/acetone 15:1), evaporated and
extracted with cyclohexane. The extract was discarded and the remaining
solid extractively recrystallized from chloroform to yiel a red solid (100 mg,
49%): M.p. >3508C; Rf (silica gel, CHCl3/n-butanol 40:1) ˆ 0.16; Rf (silica
gel, CHCl3/acetone 15:1) ˆ 0.59; IR (KBr): nÄ ˆ3070w, 2954m, 2927s,
2856m, 1698s, 1660s, 1594s, 1435m, 1405s, 1356m, 1344m, 1325s, 1265m,
1212w, 1175w, 852w, 811s, 751m, 745 cmÀ1 m; 1H NMR (400 MHz, CDCl3,
258C, TMS): d ˆ 0.78 (t, 12H; 4CH3), 1.21 (m, 32H; 16CH2), 1.77 (m, 4H;
a-CH2), 2.13 (m, 4H; a-CH2), 5.07 (m, 2H; 2CH), 6.72 (s, 2H; R2N-CH2-
NR2), 8.48 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.50 (d, 3J(H,H) ˆ
8.1 Hz, 4H; 4CH perylene), 8.57 (brs, 2H; 2CH perylene), 8.67 (d,
3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene); 13C NMR (CDCl3): d ˆ 14.01 (4C,
CH3), 22.55, 26.94, 29.18, 31.75, 32.29 (20C, CH2), 38.73 (1C, CH2), 54.80
(1C, CH), 122.81, 123.01, 123.08, 126.17, 126.38, 128.80, 129.35, 130.86,
N-(1-Hexylheptyl)-N'-(aminocarbonyl-2'-anthraquinonyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (15a): N-(1-Hexylheptyl)-N'-(amino)-
perylene-3,4:9,10-tetracarboxylic bisimide (150 mg, 0.26 mmol) and an-
thraquinone-2-carboxylic chloride (140 mg, 0.52 mmol) were allowed to
react according to the general procedure and purified by two extractive
recrystallizations (toluene and chloroform) to yield a reddish brown
powder (160 mg, 73%). M.p. >3608C; Rf (silica gel, CHCl3/acetone
15:1) ˆ 0.46; Rf (Al2O3 N II, CHCl3/acetone 15:1) ˆ 0.47; IR (KBr): nÄ
ˆ3350w (NH), 3080w, 2927m, 2856m, 1724w, 1697s, 1658s, 1594s, 1404m,
1
1347s, 1253s, 1173m, 810s, 740s, 709 cmÀ1 s; H NMR (400 MHz, CDCl3,
258C, TMS): d ˆ 0.82 (t, 6H; 2CH3), 1.27 (m, 16H; 8CH2), 1.89 (m, 2H; a-
CH2), 2.27 (m, 2H; a-CH2), 3.66 (s, 1H; 1NH), 5.20 (m, 1H; 1CH), 7.84 (m,
2H; 2CH anthraquinone), 8.38 (m, 2H; 2CH anthraquinone), 8.50 (brs,
3
2H; 2CH anthraquinone), 8.63 (d, J(H,H) ˆ 8.4 Hz, 2H; 2CH perylene),
8.67 (d, 3J(H,H) ˆ 8.6 Hz, 2H; 2CH perylene), 8.75 (d, 3J(H,H) ˆ 8.0 Hz,
4H; 4CH perylene), 8.96 (s, 1H; 1-H anthraquinone); UV/Vis (CHCl3):
lmax (e) ˆ 259 (76660), 276 sh (18390), 331 br. (9410), 367 (6820), 434 sh
(7430), 460 (22530), 491 (59700), 528 nm (97860); fluorescence (CHCl3):
lmax (Irel) ˆ 535 (1.00), 577 (0.54), 627 nm (0.13); MS (70 eV): m/z (%): 822
ˆ
131.68, 134.07, 134.78 (40C, CH perylene), 162.99 (8C, C O perylene);
UV/Vis (CHCl3): lmax (e) ˆ 370 (6160), 434 sh (8170), 460 (32390), 492
(94330), 532 nm (174560); fluorescence (CHCl3): lmax (Irel) ˆ 538 (1.00),
‡
‡
‡
(5) [M ‡H], 821 (9) [M ], 641 (9), 640 (24), 639 (30) [M À C13H26], 588
‡
‡
(6), 587 (15), 407 (16), 406 (60), 405 (100) [M À C13H26 À C15H6O3], 391
580 (0.40), 631 nm (0.08); MS (70 eV): m/z (%): 1157 (0.6) [M ], 974 (1)
‡
‡
‡
(6), 390 (10), 377 (11), 376 (31), 251 (11), 250 (7), 249 (40), 236 (12), 235
(70), 221 (13), 207 (13); elemental analysis calcd (%) for C52H43N3O7
(821.9): C 75.99, H 5.27, N 5.11; found: C 76.29, H 5.67, N 5.34.
[M À C13H26], 793 (3) [M À C26H42], 404 (2) [C25H12N2O4 ], 391 (6), 390
‡
‡
(8) [C24H10N2O4 ], 374 (1), 182 (46)[C13H26 ]; elemental analysis calcd (%)
for C75H72N4O8 (1157.4): C 77.83, H 6.27, N 4.84; found: C 77.62, H 6.29, N
4.78.
N-(1-Hexylheptyl)-N'-(aminocarbonyl-2'-fluorene-9-onyl)-perylene-
3,4:9,10-tetracarboxylic bisimide (15b): N-(1-Hexylheptyl)-N'-(amino)-
perylene-3,4:9,10-tetracarboxylic bisimide (100 mg, 0.17 mmol) and fluo-
rene-9-on-2-carboxylic chloride (120 mg, 0.49 mmol) were allowed to react
according to the general procedure and purified by an extractive
N-(1-Hexylheptyl)-N'-(methyl-9'-anthracenyl)-perylene-3,4:9,10-tetracarb-
oxylic bisimide) (10c): N-(1-Hexylheptyl)-perylene-3,4:9,10-tetracarbox-
ylic bisimide (100 mg, 0.17 mmol), 9-(bromomethyl)-anthracene (80 mg,
0.30 mmol) and potassium carbonate (650 mg, 4.70 mmol) in anhydrous
DMF (10 mL) was allowed to react according to the general procedure
(10% KOH was replaced by 20 mL of distilled water) and purified by
column separation (silica gel, chloroform; separation of a violet forerun
from the broad red main fraction) and an extractive recrystallization from
cyclohexane to yield a violet powder (30 mg, 23%). M.p. 209 2118C; Rf
recrystallization from chloroform to yield
a reddish orange powder
(50 mg, 37%). M.p. >3608C; Rf (silica gel, CHCl3/acetone 15:1) ˆ 0.28;
IR (KBr): nÄ ˆ3070w, 2927m, 2856m, 1722s, 1697s, 1660s, 1616w, 1594s,
1579w, 1458w, 1404m, 1347m, 1306w, 1255m, 1176w, 810m, 740 cmÀ1 m;
UV/Vis (CHCl3): lmax (e) ˆ 261 (93070), 270 (85790), 298 sh (10990), 314 sh
5642
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0947-6539/02/0824-5642 $ 20.00+.50/0
Chem. Eur. J. 2002, 8, No. 24

Bichromophoric Perylene Derivatives
5630 5643
(silica gel, CHCl3) ˆ 0.19; IR (KBr): nÄ ˆ 3050w, 2954m, 2926m, 2856m,
1698s, 1658s, 1594s, 1579m, 1447w, 1434w, 1405m, 1378w, 1334m, 1250w,
1171w, 810s, 749m, 731 cmÀ1 w; 1H NMR (400 MHz, CDCl3, 258C, TMS):
d ˆ 0.81 (t, 6H; 2CH3), 1.26 (m, 16H; 8CH2), 1.86 (m, 2H; a-CH2), 2.24 (m,
2H; a-CH2), 5.17 (m, 1H; 1CH), 6.39 (s, 2H; 1CH2), 7.44 (t, 3J(H,H) ˆ
8.0 Hz, 2H; 2CH anthracene), 7.53 (dt, 3J(H,H) ˆ 9.0 Hz, 4J(H,H) ˆ 1.3 Hz,
2H; 2CH anthracene), 8.00 (d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH anthracene),
8.45 (s, 1H; 5-H anthracene), 8.50 (d, 3J(H,H) ˆ 8.2 Hz, 2H; 2CH
perylene), 8.54 (d, 3J(H,H) ˆ 8.8 Hz, 2H; 2CH perylene), 8.58 (d,
[3] T. J. Meyer, Progr. Inorg. Chem. 1983, 30, 441.
[4] M. D. Newton, N. Sutin, Ann. Rev. Phys. Chem. 1984, 35, 437.
[5] G. J. Kavarnos, N. J. Turro, Chem. Rev. 1986, 86, 401 449.
[6] Photoinduced electron transfer, Parts A D (Eds.: M. A. Fox, M.
Chanon), Elsevier, Amsterdam, 1988.
[7] Photoinduced electron transfer, Vols. I V (Ed.: J. Mattay), in Top.
Curr. Chem. 1990, 156; 1990, 158; 1991, 159; 1992, 163; 1993, 168;
Springer, Berlin.
[8] F. W¸rthner, Nachr. Chem. Tech. Lab. 2001, 49, 1284 1288, 1290
[Chem. Abstr. 2002, 136, 168952].
3
3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.61 (d, J(H,H) ˆ 9.0 Hz, 2H; CH
anthracene), 8.63 (m, 2H; 2CH perylene); 13C NMR (CDCl3): d ˆ 13.99
(2C, CH3), 22.54, 26.90, 29.18, 31.72, 32.36 (10C, CH2), 38.18 (1C, CH2-
NR'2), 54.77 (1C, CH), 122.89, 123.12, 123.19, 124.73, 124.77, 126.04, 126.33,
126.35, 128.06, 128.48, 129.24, 129.51, 131.08, 131.37, 131.75, 134.27, 134.74
[9] S. Hecht, J. M. J. Frechet, Angew. Chem. 2001, 113, 76 94; Angew.
¬
Chem. Int. Ed. 2001, 40, 74 91.
[10] J. Deisenhofer, O. Epp, K. Miki, R. Huber, H. Michel, J. Mol. Biol.
1984, 180, 385.
ˆ
(34C, Ar), 163.88 (4C, C O perylene); UV/Vis (CHCl3): lmax (e) ˆ 260
[11] G. McDermott, S. M. Prince, A. A. Freer, A. M. Hawthornthwaite-
Lawless, M. Z. Papiz, R. J. Cogdell, N. W. Isaacs, Nature 1995, 374,
517 521.
[12] M. S. Vollmer, F. W¸rthner, F. Effenberger, P. Emele, D. U. Meyer, T.
Stumpfig, H. Port, H. C. Wolf, Chem. Eur. J. 1998, 4, 260 269.
[13] F. W¸rthner, M. S. Vollmer, F. Effenberger, P. Emele, D. U. Meyer, H.
Port, H. C. Wolf, J. Am. Chem. Soc. 1995, 117, 8090 8099.
[14] F. Effenberger, H. Schlosser, P. Baeuerle, S. Maier, H. Port, H. C.
Wolf, Angew. Chem. 1988, 100, 274 277; Angew. Chem. Int. Ed. Engl.
1988, 27, 281.
[15] Review: H. Langhals, Heterocycles 1995, 40, 477 500.
[16] H. Langhals, J. Karolin, L. B.-ä. Johansson, J. Chem. Soc. Faraday
Trans. 1998, 94, 2919 2922.
[17] Compare: N. Nijegorodov, R. Mabbs, Spectrochim. Acta A 2001, 57,
1449 1462.
[18] H. Langhals, S. Demmig, H. Huber, Spectrochim. Acta 1988, 44A,
1189 1193.
[19] D. L. Dexter, J. Chem. Phys. 1953, 21, 836 850.
[20] N. J. Turro, Modern Molecular Photochemistry, Benjamin Cummings,
Menlo Park, 1978, pp. 297 361.
[21] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733
748.
[22] S. Demmig, H. Langhals, Chem. Ber. 1988, 121, 225 230.
[23] H. Langhals, Ger. Offen. DE 3016764 (April 30, 1980) [Chem. Abstr.
1982, 96, P70417x].
(122100), 351 (8286), 369 (11930), 390 (10120), 433 sh (5380), 460 (18130),
492 (49170), 528 nm (80760); fluorescence (CHCl3): lmax (Irel) ˆ 534 (1.00),
‡
578 (0.53), 626 nm (0.13); MS (70 eV): m/z (%): 763 (51) [M ‡H], 762 (90)
‡
‡
[M ], 582 (9), 581 (21), 580 (19) [M À C13H26], 572 (9), 392 (5), 391 (18),
‡
390 (31) [M À C13H26 À C15H10], 373 (4), 346 (4), 345 (3), 192 (36), 191
‡
(100), 190 (18) [C15H10 ], 189 (24); elemental analysis calcd (%) for
C52H46N2O4 (763.0): C 81.86, H 6.08, N 3.67; found: C 81.81, H 6.12, N 3.67.
N-(1-Hexylheptyl)-N'-(methyl-2-anthraquinoyl)-perylene-3,4:9,10-tetra-
carboxylic bisimide) (10a): N-(1-Hexylheptyl)-perylene-3,4:9,10-tetracar-
boxylic bisimide (200 mg, 0.35 mmol), 2-(bromomethyl)-anthraquinone
(200 mg, 0.66 mmol) and potassium carbonate (1.3 g, 9.4 mmol) in anhy-
drous DMF (20 mL) were allowed to react according to the general
procedure (10% KOH was replaced by 20 mL of distilled water) and
purified by column separation (silica gel, chloroform; separation of a red
forerun) to yield a red powder (40 mg, 14%). M.p. 342 3458C; Rf (silica
gel, CHCl3/acetone 15:1) ˆ 0.86; Rf (Al2O3 N I, CHCl3/acetone 15:1) ˆ
0.47; IR (KBr): nÄ ˆ3070w, 2954m, 2927m, 2856m, 1697s, 1660s, 1594s,
1580m, 1437m, 1405m, 1378w, 1339s, 1294m, 1172m, 811m, 743w,
712 cmÀ1 m; 1H NMR (400 MHz, CDCl3, 258C, TMS): d ˆ 0.79 (t, 6H;
2CH3), 1.34 (m, 16H; 8CH2), 1.85 (m, 2H; a-CH2), 2.23 (m, 2H; a-CH2),
5.16 (m, 1H; 1CH), 5.54 (s, 2H; 1CH2), 7.73 (t, 3J(H,H) ˆ 6.4 Hz, 1H; 6-H
3
4
or 7-H anthraquinone), 7.90 (dd, J(H,H) ˆ 8.1 Hz, J(H,H) ˆ 1.8 Hz, 1H;
3-H anthraquinone), 8.23 (d, 3J(H,H) ˆ 7.3 Hz, 1H; 5-H or 8-H anthraqui-
3
none), 8.25 (d, J(H,H) ˆ 7.8 Hz, 1H; 5-H or 8-H anthraquinone), 8.25 (d,
3J(H,H) ˆ 8.0 Hz, 1H; 4-H anthraquinone), 8.36 (d, 4J(H,H) ˆ 1.4 Hz, 1H;
1-H anthraquinone), 8.59 (d, 3J(H,H) ˆ 8.2 Hz, 2H; 2CH perylene), 8.60
(d, 3J(H,H) ˆ 8.1 Hz, 2H; 2CH perylene), 8.67 (d, 3J(H,H) ˆ 7.9 Hz, 4H;
4CH perylene); COSY NMR: cross-peaks at d ˆ (7.73, 8.23, 8.25), (7.90,
8.25), (7.90, 8.36); 13C NMR (CDCl3): d ˆ 14.01 (2C, CH3), 22.57, 26.94,
29.21, 31.76, 32.40 (10C, CH2), 43.54 (1C, CH2-NR2), 54.85 (1C, CH),
122.77, 123.01, 123.36, 126.86, 127.16, 127.18, 127.51, 127.75, 128.19, 129.50,
129.53, 129.62, 131.92, 132.74, 133.04, 133.46, 133.53, 133.73, 134.02, 134.04,
134.19, 134.57, 134.61, 135.23, 143.80 (32C, CH anthraquinone, CH
[24] H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124, 529 535.
[25] H. Langhals, W. Jona, Angew. Chem. 1998, 110, 998 1001; Angew.
Chem. Int. Ed. Engl. 1998, 37, 952 955.
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1989, 43, 6 9.
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7, 2245 2253.
[33] We thank Prof. L. B.-ä. Johansson for the University of Umea for
these measurements.
[34] J. Walz, K. Ulrich, H. Port, H. C. Wolf, J. Wonner, F. Effenberger,
Chem. Phys. Lett. 1993, 213, 321 324.
ˆ
ˆ
perylene), 163.37 (4C, C O perylene), 182.73, 182.88 (2C, C O anthra-
quinone); UV (CHCl3): lmax (e) ˆ 258 (87740), 277 (24430), 327 br.
(10810), 436 sh (5260), 460 (17310), 491 (47230), 528 nm (78960);
fluorescence (CHCl3): lmax (Irel) ˆ 537 (1.00), 579 (0.52), 625 nm (0.12);
solid-state fluorescence: lmax ˆ 654 nm; MS (70 eV): m/z (%): 793 (14)
‡
‡
[M ‡H], 792 (23) [M ], 775 (5), 613 (7), 612 (28), 611 (78), 610 (100)
‡
[M À C13H26], 593 (6), 375 (5), 373 (15), 372 (18), 346 (18), 345 (4);
elemental analysis calcd (%) for C52H44N2O6 (792.9): C 78.77, H 5.59, N
3.53; found: C 78.60, H 5.30, N 3.13; analysis calcd for C52H44N2O6:
792.3199; found: 792.3233 (HRMS).
[35] J. M. Endtner, F. Effenberger, A. Hartschuh, H. Port, J. Am. Chem.
Soc. 2000, 122, 3037 3046.
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tional Workshop on Molecular Devices (Ed.: F. L. Carter), Marcel
Dekker, 1982/1984.
Acknowledgement
[38] J.-M. Lehn, Angew. Chem. 1990, 102, 1347 1362; Angew. Chem. Int.
Ed. Engl. 1990, 29, 1304 1319.
[39] F. M. Raymo, Adv. Mater. 2002, 14, 401 414.
[40] H. Langhals, Chem. Ber. 1985, 118, 4641 4645.
This work was supported by the Deutsche Forschungsgemeinschaft and the
Fonds der chemischen Industrie.
Received: April 3, 2002
Revised: August 8, 2002 [F3993]
[1] T. Fˆrster, Fluoreszenz organischer Verbindungen, 1st ed., Vanden-
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Chem. Eur. J. 2002, 8, No. 24
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