Angular benzoperylenetetracarboxylic bisimides

Article abstract of DOI:10.1002/chem.201103221

Benzoperylene derivatives with two angularly attached dicarboxylic imide rings, which were prepared by the Diels-Alder-Reaction, exhibit strong fluorescence and their free peri positions allow either control of the UV/Vis spectra through their substituent

Full text of DOI:10.1002/chem.201103221

FULL PAPER
DOI: 10.1002/chem.201103221
Angular Benzoperylenetetracarboxylic Bisimides
Heinz Langhals,* Bernd Bçck, Tanja Schmid, and Alexey Marchuk[a]
Abstract: Benzoperylene derivatives with two angularly attached dicarboxylic
imide rings, which were prepared by the Diels–Alder-Reaction, exhibit strong fluo-
rescence and their free peri positions allow either control of the UV/Vis spectra
through their substituents or form anchor positions for the attachment of function-
al units. The angular chromophore 3 may be used both for fluorescent labeling
such as for primary amines or enzymes or as building blocks for more complex as-
semblies where they may act as energy donors for FRET or electron acceptors in
PET such as for photovoltaic solar cells.
Keywords: electron transfer · en-
zymes · fluorescence spectroscopy ·
FRET · heterocycles
Introduction
Results and Discussion
Benzoperylene derivatives such as tetracarboxylic bisi-
mides[1] 1 and hexacarboxylic trisimides 2 (Scheme 1) re-
ceive increasing interest as energy donors[2] for FRET[3]
(Fçrster resonance energy transfer)[4] processes.
The hitherto unknown angular isomer 3 of 1 offers new
possibilities such as an orthogonal arrangement of the sub-
stituents R and the possibility of the extension of the struc-
ture at the unsubstituted peri-positions. Thus, it forms an in-
teresting building block for more complex molecular archi-
tectures where the orthogonal arrangement of chromo-
phores[2,5] allows the special management of the energy of
optical excitation.
We started the synthesis of 3 with perylene-3,4-dicarboxylic
imide[6] (4) where the solubilising 1-hexylheptyl swallow-tail
substituent was attached to the nitrogen atom and allowed
for a reaction with maleic anhydride and the aromatizing re-
agent p-chloranile according to the Clar variant[7] of the
Diels–Alder-reaction. We obtained the readily soluble anhy-
dride carboximide 5 in 87% yield (see Scheme 2). Com-
Scheme 1. Benzoperylenetetracarboxylic bisimides (1), benzoperylene-
hexacarboxylic trisimides (2) and angular benzoperylenetetracarboxylic
bisimides (3).
[a] Prof. Dr. H. Langhals, Dr. B. Bçck, M. Sc. T. Schmid, A. Marchuk
Department of Chemistry
LMU University of Munich
Butenandtstr. 13, 81377 Munich (Germany)
Fax : (+49)89-2180-77640
E-mail: Langhals@lrz.uni-muenchen.de
Scheme 2. Preparation of the angular perylenebiscarboximdes 3. i) Maleic
anhydride, p-chloranile. ii) R-NH2, quinoline and imidazole, respectively.
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pound 5 forms a key intermediate for further synthesis and
has not been described before; another low soluble and dif-
ficult to purify derivative of the basic chromophore of 5 has
been reported, however, with different spectroscopic data.[8]
Compound 5 was condensed with primary amines to prepare
3 where the two swallow-tail substituents in 3a made the
material very readily soluble. The introduction of the bulky
tert-butyl substituent in 3m or the rigid cyclohexyl substitu-
ent in 3p proceeded without problems. Moreover, function-
alities such as for labeling can be introduced by means of a
substituent R in 3. For example, a hydroxy group can be in-
corporated by condensation of 5 with aminohydroxy-p-
xylene to form 3b, a carboxyl group by the condensation of
4-aminobenzoic acid to prepare 3c and a basic and nucleo-
philic amino group, respectively, in 3d where the latter is a
suitable building block for the synthesis of even more com-
plex structures by condensation. The introduction of an al-
dehyde group (3e and 3g with differently long aromatic
spacers) offers many possibilities for the labeling of biologi-
cally active materials with primary amino groups. A direct
condensation of aminoaldehydes with 5 is problematic be-
cause of polymerisation. Thus, we protected the aldehyde
group as the ethylene acetal according to ref. [9] and pre-
pared either aldehyde 3e directly by means of the corre-
sponding amino acetals and acidic workup or acetal 3 f if
acid was excluded. The former (3e) is more appropriate for
direct labeling such as in the condensations with primary
amines, whereas the latter is useful as a protected compound
as it allows for the long-term storage of the comparably re-
active aldehyde. The oxidation of 3b is an alternative for
the preparation of 3e. The even longer spacer in 3g and 3h,
respectively, allows more distance between the chomophore
and the labelled position and lowers interference by the la-
beling.
Scheme 3. Synthesis of azomethines 6 by means of the aldehydes 3e (n=
1) and 3g (n=2), respectively.
they do not interfere with the catalytic activity of catalase,
whereas DMSO favors labeling indicated by a yellow colo-
ration, though it destroys the catatlytic activity. Best results
were obtained with NMP giving an efficient labeling and
preserving the enzymatic activity indicated by a vigorous
evolution of oxygen from hydrogen peroxide. Other alde-
hyde-linked chromophores gave similar results so that NMP
seems to be an ideal solvent for the labeling of enzymes and
other peptides with lipophilic aldehydes-linked chromo-
phores.
The free peri position in 3 and 5, respectively, can be ap-
plied for the construction of even more complex assemblies.
Bromination of 3 gave a complex mixture, which was diffi-
cult to separate. Better results were obtained if 4 was firstly
halogenated to form 7 and then extended by means of the
Clar reaction to form 8 and 9 (Scheme 4). Clearly, only
The condensation of 3e and 3g with aromatic amines 6a
and 6b, respectively, is as simple as the reaction with simple
aliphatic amines 6c and 6d and
amino acids 6e and 6 f; see
Scheme 3. The labeling of natu-
ral polypeptides requires a suit-
able solvent for both the pep-
tide and the labeling agent 3e
and 3g. We applied bovine
serum catalase as a typical bio-
logically active substrate and in-
vestigated 3e and 3g in various
solvents where NMP gives com-
parably good results. The cata-
lase is labelled in both cases,
which is indicated by its colora-
tion, and remains catalytically
active. Good results were also
obtained in DMF, N,N-dimeth-
ylacetamide and N-methylpi-
peridone. DMPU, DMEU and
N-methylformanilide are not
Scheme 4. Synthesis of the peri-halogenated compound 7. i) Br2, K2CO3, and chlorobenzene for 7a and I2,
useful for labeling, although H5IO6, HOAc and H2SO4, CHCl3 for 7b.
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Benzoperylenetetracarboxylic Bisimides
FULL PAPER
these two isomers were formed, however they could not be
separated, neither the bromine derivative 8a and 9a, respec-
tively, nor the iodine derivatives 8b and 9b. The purification
problems could be overcome by a double substitution in the
peri position.
We then nitrated 4 with nitric acid and acetic anhydride
to dinitro derivative 10 where the Clar reaction with maleic
anhydride to form 11 proceeded more slowly than the reac-
tion with 4 because of electron deficiency; the conversion to
11 was successful without any problems. Compound 12
(Scheme 5) was expected as the product of reduction of 11
by means of metallic iron and HCl/ethanol (Bechamp reduc-
tion), although amidine 13 was obtained instead and did not
undergo further reduction (see Scheme 6). Finally, a reduc-
tion of 11 to 12 was successful by means of H2 and Pd/C
where hydroxylamine 14 was the main product in a 70:30
mixture with 12.
where the structure was stabilized by the incorporation into
a six-membered ring and the application of geminal methyl
groups. No oxidation of the aliphatic structure was found as
observed in ref. [10]; on the other hand, the condensation
was carried out with a strict exclusion of atmospheric
oxygen. The chromophore was further extended by the con-
densation of 5 with 1,8-diaminonaphthalene to form 16
(Scheme 7).
Scheme 7. Amidines 15 and 16.
The successful labeling of amines with 3g and 3e, respec-
tively, was extended to the chromophore of 2. As a conse-
quence, we prepared aldehyde 17a for n=1 and 17b for n=
2 both as the free aldehydes and protected as the ethylene
acetals (17c and 17d, respectively) and condensed the alde-
hydes to form azomethines 18 similar to 6; see Scheme 8.
Catalase could be labelled with 17 and NMP can be recom-
mended analogously to 3e and 3g. Moreover, we prepared
the dicarboxylic imide aldehydes 19a for n=1 and 19b for
n=2 where a labeling was successful even without the solu-
bilising sec-alkyl group; see Scheme 9. Red compounds 20
were obtained both from simple primary amines and cata-
lase.
Scheme 5. Synthesis of the peri-dinitrated compound 11 and the diamine
12. i) Maleic anhydride, chloranile. ii) H2, Pd/C.
Finally, two chromophores of 3 were interlinked by con-
densation of 1,4-diaminotetramethyl benzene where a mix-
ture of 21 and 22 was obtained which was difficult to sepa-
rate even in TLC (Scheme 10).
The UV/Vis absorption spectrum of 5 is hypsochromically
shifted compared with 1 and structured differently (see
Figure 1). The vibronic structure of 5 is less pronounced,
however, there are several optical transitions in the visible
where the most bathochromic is not the most intense one.
The fluorescence spectrum is slightly structured with a fluo-
rescence quantum yield of 64%.
The UV/Vis spectra of tetracarboxylic bisimide 3a resem-
ble the spectra of 5, are slightly more structured and differ
completely from the spectra of isomeric 1 where vibronic
bands are dominating. On the other hand, several electronic
transitions can be seen in Figure 2 where the most batho-
chromic is not the most intense one. The fluorescence quan-
tum yield of 3a is 31% and thus, is about the half that of 5,
however, still gives a strong visible impression in day light.
Scheme 6. Amidine 13 was obtained from the nitro compound 11 and Fe/
HCl, whereas the hydroxylamine 14 and the amino compound 12 (70:30)
from the catalytic reduction (H2/Pd).
The anhydride group in 5 was used for a further extension
of the chromophore. A condensation with 1,3-diamino-2,2-
dimethylpropane gave amidine 15 analogously to ref. [10],
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H. Langhals et al.
The labeling of primary amines and proteins with the deriv-
atives 3e and 3g, respectively, influences the UV/Vis spectra
insignificantly compared with 3a.
The introduction of the electron-withdrawing nitro groups
into the peri-position of 3 to form 11 shifts the UV/Vis spec-
tra only slightly, induces a stronger vibronic structure and
diminishes the fluorescence
quantum yield to 12%, whereas
the electron-donating amino
groups in 12 and the hydroxyla-
mino groups in 14 cause strong-
ly bathochromic shifts so that
dark purple solutions were ob-
tained. Amidine 13 is strongly
solvatochromic both in absorp-
tion and fluorescence. Batho-
chromic shifts were also in-
duced by the introduction of
the aromatic amidine units in
16; see Figure 3. The linking of
two unis of 3 to form the dyads
21 and 22, respectively, causes
weak exciton interactions with
slightly altered spectra and a
nearly unaffected fluorescence
quantum yield of 36%.
Scheme 8. Synthesis of azomethines 18 by means of the aldehydes 4e and 4g, respectively.
Photophysical properties of
the preylene derivatives were
reported in Table 1. The fluo-
rescence lifetimes of 3 are in the order of 6–7 ns and corre-
spond to the absorptivities of 30000–40000. There is a pro-
nounced inter-system crossing (ISC) in 3a competing with
fluorescence so that phosphorescence can be observed and
efficient formation of singelt oxygen with a quantum yield
as high as 68%; for more details see ref. [11].
Chromophore 3 is an interesting building block for even
more complex arrangements of optical units. As a conse-
quence, we used aldehyde 3e, allowed an acid-catalysed re-
action with the corresponding dipyrrolomethane and a sub-
sequent oxidation with p-chloranile and isolated the corrole
dyad 3q (Figure 4); for corroles see ref. [12]. A similar reac-
tion was successful with benzoperylene aldehyde 17a to
form 23.
Scheme 9. Synthesis of azomethines 20 by means of the aldehydes 19.
The UV/Vis absorption spec-
trum of 3q is dominated by the
strong absorption of the benzo-
perylene and the Q-band of the
corrole unit below 500 nm and
indicated the formation of the
dyad with its appreciably
weaker bathochromic absorp-
tion of the corrole with the
soret bands; see Figure 4. Effi-
cient energy transfer from the
hypsochromically
benzoperylen proceeds to the
corrole with fluorescence
absorbing
a
quenching of the former. The
fluorescence of the corrole unit
of 3q is comparably weak
Scheme 10. Dyads 21 and 22.
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Benzoperylenetetracarboxylic Bisimides
FULL PAPER
viously, the even more electron
depleted benzoperylene triscar-
boximide causes in 23 a more
efficient PET than in 3q. Such
PET processes cause light-in-
duced charge separation[14] and
are of interest for photovoltaics
in solar cells[15] where the
charge separation by 3q and 23
is induced by a purely organic
assembly.
Conclusion
The angular isomers 3 of the
benzoperylenetetracarboxylic
bisimides 1 enlarge not only the
variety of perylene derivatives,
where about 3% was found in chloroform solution. There is
an efficiently competing photo-induced electron transfer
process (PET) from the electron-rich corrole to the benzo-
perylene unit; compare ref. [13]. A similar behaviour was
observed for the dyad 23 (Figure 5). An efficient energy
transfer proceeds fom the benzoperylenetriscarboximide to
the corrole where only a weak fluorescence is observed for
the latter with a fluorescence quantum yield below 1%; ob-
but also open many novel possibilities in this field. They ex-
hibit strong fluorescence and their free peri positions allow
either the controlling of UV/Vis spectra by means of sub-
stituents or form anchor positions for the attachment of
functional units. The angular chromophore 3 may be used
both for fluorescent labeling such as for primary amines or
enzymes or as building blocks for more complex assemblies
Figure 3. UV/Vis absorption (left) and fluorescence (right) spectra of 16
in chloroform.
Figure 1. UV/Vis absorption (left) and fluorescence (right) spectra of 5 in
Table 1. Photophysical properties of perylene derivatives. Molar absorp-
tivities in the visible (e), fluorescence quantum yields (F) and fluores-
cence lifetimes (t).
Compound
e[a]
F[b]
t[c]
Solvent
[d]
3a
3e
3i
3k
4
5
10
11
28400
31300
22900
43600
32000
25500
56000
39000
60200
24000
0.31
0.30
0.38
0.21
ꢀ1.00
0.64
ꢀ1.00
0.12
0.17
0.91
0.36
6.7
7.1
6.1
6.4
6.1
6.6
5.3
2.4
7.0
6.3
5.0
CH2Cl2
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
17a
19a
21/22
Figure 2. UV/Vis absorption (left) and fluorescence (right) spectra of 3a
in chloroform.
[a] Molar absorptivity im molLÀ1 cmÀ1. [b] Fluorescence quantum yield.
[c] Fluorescence lifetime in ns. [d] See ref. [11b]
chloroform.
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H. Langhals et al.
2854.3 (s), 2361.6 (vs), 2337.7 (vs), 1702.1 (s), 1661.5 (s), 1605.4 (m),
1558.4 (m), 1457.7 (m), 1428.4 (m), 1396.0 (m), 1325.3 (m), 1111.7 (w),
796.0 (w), 667.9 cmÀ1 (w); UV/Vis (CHCl3): lmax (Erel)=350.8 (0.31),
366.0 (0.52), 413.0 (1.00), 433.8 (0.83), 473.9 (0.13), 567.2 (0.11), 608.0
(0.08), 639.6 (0.06), 715.6 nm (0.01); fluorescence (CHCl3, lexc =366 nm):
lmax (Irel)=535.8 (0.03), 663.1 (1.00), 720.4 nm (0.36); fluorescence quan-
tum yield (CHCl3, lexc =565 nm, E565 nm/1 cm =0.0111, reference S-13 with
F=1.00): F=0.0212. Fluorescence quantum yield (CHCl3, lexc =350 nm,
E
350 nm/1 cm =0.0307, reference S-13 with F=1.00): F=0.018. MS (FAB+):
m/z (%): 1274 (1) [M+H]+, 1273 (2) [M]+, 1272 (2) [MÀH]+, 1271 (1),
1092 (0.3) [M+HÀC13H26]+, 1091 (0.3) MÀC13H26]+, 1090 (0.3)
[MÀHÀC13H26]+, 675 (0.5) [corrole+benzyl spacer]+; HMRS (FAB+):
calcd for C77H59Cl4N6O4 [M+H]+: 1273.3345, found 1273.3331, D=
0.0014.
10-[N,N’’-Bis(1-hexylheptyl)-N’-(benzyl)benzo
tris(dicarboximide]-5,15-bis(2,6-dichlorophenyl)corrole (23): N,N’’-Bis(1-
hexylheptyl)-N’-(4-formylbenzyl)benzo[ghi]perylene-1’,2’:3,4:9,10-tris(di-
ACHTUNGTRNE[NUNG ghi]perylene-1’,2’:3,4:9,10-
Figure 4. UV/Vis absorption (left) and fluorescence (right) spectra of 3q
in chloroform (c), compared with 3a (a).
AHCTUNGTRENNUNG
carboximide) (17a, 134 mg, 139 mmol), 2,6-dichlorophenyldipyrrome-
thane (81.0 mg, 278 mmol), dichloromethane (5.00 mL), TFA (6.34 mg,
55.6 mmol in 0.20 mL CH2Cl2), triethylamine (5.63 mg, 55.6 mmol in
0.25 mL CH2Cl2) and p-chloranile (103 mg, 417 mmol) were allowed to
react analogously to 3q, purified by column separation (silica gel 63–
200 mm, CH2Cl2, first greene fraction), dissolved in a small amount of
CHCl3 and precipiated with methanol. Yield 35.0 mg (16.5%) green
solid, m.p. ꢀ2508C; Rf (silica gel, CH2Cl2) = 0.80; 1H NMR (600 MHz,
CDCl3): d=À2.94–2.78) (brs, 3H, NH), 0.80 (t, 3J=7.0 Hz, 12H, CH3),
1.17–1.34 (m, 32H, CH2CH2CH2CH2CH3), 1.89–1.98 (m, 4H, CHCH2),
2.28 À2.39 (m, 4H, CHCH2), 5.25–5.36 (m, 2H, NCH2), 5.46 (s, 2H,
NCH), 7.63–7.70 (m, 2H, Harom), 7.71–7.82 (m, 3H, Harom), 8.04 (d, 3J=
8.3 Hz, 2H, Harom), 8.19–8.29 (m, 2H, Harom), 8.50–8.77 (m, 5H, Harom),
9.08 (s, 1H, Harom), 9.11–9.25 (m, 4H, Harom), 9.36–9.42 (m, 1H, Harom),
9.44 (d, 3J=8.3 Hz, 2H, HBP), 10.57 ppm (s, 2H, HBP); IR (ATR): n˜
=3357.9 (m), 3077.4 (w), 2953.6 (s), 2926.3 (vs), 2856.4 (s), 1770.1 (w),
1709.9 (s), 1689.3 (vs), 1679.4 (vs), 1664.4 (vs), 1595.3 (w), 1572.3 (m),
1557.9 (w), 1428.1 (w), 1414.5 (w), 1397.0 (w), 1364.3 (w), 1318.2 (m),
1238.0 (w), 1111.3 (m), 812.0 (w), 756.1 (w), 712.5 cmÀ1 (w); UV/Vis
(CHCl3): lmax (Erel)=272.4 (0.34), 377.6 (0.55), 418.7 (1.00), 431.0 (0.79),
467.1 (0.61), 567.6 (0.08), 606.4 (0.05), 717.2 nm (0.02); fluorescence
(CHCl3, lexc =378 nm, very weak fluorescence): lmax (Irel)=476.7 (1.00),
512.2 (0.76), 550.1 (0.29), 651.1 (0.22), 723.8 nm (0.23); fluorescence
(CHCl3, lexc =419 nm, very weak fluorescence): lmax (Irel)=477.6 (1.00),
508.6 (0.70), 651.4 (0.65), 720.9 nm (0.79); fluorescence quantum yield
(CHCl3, lexc =569 nm, E569 nm/1 cm =0.0079, reference S-13 with F=1.00):
F=0.0014, Fluorescence quantum yield (CHCl3, lexc =378 nm, E378 nm/
1 cm =0.0439, reference S-13 with F=1.00): F=0.0021. MS (FAB+): m/z
(%): 1525 (1) [M+H]+,1524 (1) [M]+, 1523 (1) [MÀH]+, 1343 (0.3)
[M+HÀC13H26]+, 1342 (0.3) [MÀC13H26]+, ###1341 (0.3) [M-H-C13H26]+,
1160 (0.2) [M-2. C13H26]+, 1159 (0.2) [MÀHÀ2ꢁC13H26]+, 675 (0.4) [cor-
role+benzyl spacer]+; HMRS (FAB+): calcd for C92H84Cl4N7O6 [M+
H]+: 1524.5237, found 1524.5215, D=0.0022; elemental analysis (%)
calcd for C92H83Cl4N7O6 (1524.5): C 72.48, H 5.49, Cl 9.30, N 6.43; found
C 72.00, H 5.62, Cl 8.86, N 6.19.
Figure 5. UV/Vis absorption spectrum of 23 in chloroform.
where they may be energy donor for FRET or electron ac-
ceptors in PET such as for photovoltaic solar cells.
Experimental Section
General methods: See Supporting Information.
10-[N-(1-Hexylheptyl)-N’-(benzyl)benzo
boximide)]-5,15-bis(2,6-dichlorophenyl)corrole (3q): N-(1-Hexylheptyl)-
N’-(4-formylbenzyl)benzo[ghi]perylene-3,4,6,7-bis(dicarboximide) (3e,
ACHTUNGTRENN[UNG ghi]perylene-3,4,6,7-bis(dicar-
AHCTUNGTRENNUNG
200 mg, 280 mmol) and 2,6-dichlorophenyldipyrromethane (163 mg,
560 mmol) were dissolved with the exclusion of light in dichlormethane
(7.00 mL), treated with trifluoroacetic acid (TFA, 12.8 mg, 112 mmol, dis-
solved in 0.25 mL of CH2Cl2), stirred at room temperature for 20 min,
treated with triethylamine (11.3 mg, 112 mmol) and then p-chloranile
(207 mg, 840 mmol), stirred at room temperature for 24 h, evaporated in
vacuo, purified by column separation (silica gel 63–200 mm, CH2Cl2, first
green band, and then silica gel, CH2Cl2/n-hexane 10:1), dissolved in a
small amount of CH2Cl2 and precipitated with n-pentane. Yield 35.0 mg
The other compounds including characterization can be found in the Sup-
porting Information.
1
(10%) green solid, m.p. >4008C. Rf (silica gel, CH2Cl2) = 0.85; H NMR
(600 MHz, CDCl3): d=À2.91–2.79 (brs, 3H, NH), 0.81 (t, 3J=7.0 Hz,
6H, CH3), 1.22–1.27 (m, 16H, CH2CH2CH2CH2CH3), 1.95–2.03 (m, 2H,
CHCH2), 2.32–2.44 (m, 2H, CHCH2), 5.26–5.37 (m, 2H, NCH2), 5.41 (s,
1H, NCH), 7.65 (d, 3J=7.9 Hz, 2H, HCl-phenyl), 7.69–7.77 (m, 2H, HMIM-
BP), 7.83–7.89 (m, 1H, Harom), 8.03–8.12 (m, 3H, Harom), 8.22 (d, 3J=
4.3 Hz,1H, Harom), 8.32–8.35 (m, 1H, Harom), 8.36–8.40 (m, 1H, Harom),
8.45–8.49 (m, 1H, Harom), 8.51–8.54 (m, 1H, Harom), 8.60 (d, 3J=4.8 Hz,
1H, Harom), 8.68 (d, 3J=4.7 Hz, 1H, Harom), 8.75 (d, 3J=4.3 Hz, 1H,
Harom), 9.09–9.11 (m, 1H, Harom), 8.99–9.07 (m, 2H, Harom), 9.13–9.17 (m,
Acknowledgements
We thank the State of Bavaria for a scholarship (B.B.), the Fonds der
Chemischen Industrie and the CIPSM cluster in Munich for financial
support.
[1] H. Langhals, S. Kirner, Eur. J. Org. Chem. 2000, 365–380.
[2] a) H. Langhals, A. J. Esterbauer, A. Walter, E. Riedle, I. Pugliesi, J.
Am. Chem. Soc. 2010, 132, 16777–16782; b) H. Langhals, S. Poxleit-
ner, O. Krotz, T. Pust, A. Walter, Eur. J. Org. Chem. 2008, 4559–
2H,
CCHCCO); IR (ATR): n˜ =3854.1 (w), 3676.0 (w), 2951.1 (s), 2923.5 (vs),
H
arom), 9.30 (d, 3J=8.7 Hz, 1H, HMIM-BP), 10.32 ppm (s, 1H,
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FULL PAPER
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Received: October 12, 2011
Revised: April 24, 2012
Published online: && &&, 0000
Chem. Eur. J. 2012, 00, 0 – 0
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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These are not the final page numbers!

H. Langhals et al.
Two angular rings: Benzoperylene
Fluorescent Labels
derivatives with two angularly attached
dicarboxylic imide rings, which were
prepared by the Diels–Alder-Reaction,
are strongly fluorescent (see figure)
and were applied both for fluorescence
labeling (e.g., enzymes) and as compo-
nents in FRET and PET systems.
H. Langhals,* B. Bçck, T. Schmid,
A. Marchuk ................... &&&& — &&&&
Angular Benzoperylenetetracarboxylic
Bisimides
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www.chemeurj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
These are not the final page numbers!