Liquid crystalline coronene derivatives

Article abstract of DOI:10.1039/b009708j

The synthesis of liquid crystalline coronenediimides 9 and31yin Chinese) coronenemonoimide 10 is described in detail and the mesophases are investigated. A large intracolumnar charge carrier mobility of ca. 0.2 cm² Vs^-1 has been foun

Full text of DOI:10.1039/b009708j

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Liquid crystalline coronene derivatives
Ulrike Rohr,a Christopher Kohl,a Klaus Mu¨llen,*a Anick van de Craatsb and John Warmanb
aMax-Planck-Institut fu¨r Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany.
E-mail: muellen@mpip-mainz.mpg.de; Fax: z(6131)379-350
bInterfaculty Reactor Institute (IRI), Delft University of Technology, Mekelweg 15, 2629 JB
Delft, The Netherlands
Received 4th December 2000, Accepted 12th April 2001
First published as an Advance Article on the web 31st May 2001
The synthesis of liquid crystalline coronenediimides 9 and coronenemonoimide 10 is described in detail and the
mesophases are investigated. A large intracolumnar charge carrier mobility of ca. 0.2 cm2 Vs21 has been found
for the discotic mesophase of the coronenemonoimide 10 using the pulse-radiolysis time-resolved microwave
conductivity technique. The large mobility, together with the room temperature liquid crystallinity, make this
compound an attractive candidate for applications as the electron transport layer in molecular electronic
devices.
yellow compound, which was characterized as coronene
Introduction
derivative 9a. A possible explanation for the occurrence of
product 9a is a spontaneous cyclization of the expected product
14a under the reaction conditions; the detailed mechanism of
this cyclization is still unknown.
Derivatives of perylene (1) such as perylene-3,4:9,10-tetra-
carboxydiimides) 2 or perylene-3,4-dicarboximides 3 (see
Scheme 1) are important dyes and pigments due to their
outstanding chemical, thermal and photochemical stability.1 In
addition to conventional uses, perylenes 1–3 are used as so
called functional dyes in applications such as reprographic
processes,2 fluorescent solar collectors,3 photovoltaic cells,4
optical switches5 and lasers.6 With the synthesis of terrylene-
tetracarboxydiimides 47 and quaterrylenetetracarboxydiimides
5 as well as benzoylterrylenedicarboximides 68 new highly
stable dyes with attractive properties became available. In
addition, liquid crystalline perylene derivatives could be provided
such as e.g. 7 and 89 and suitably substituted perylenetetracarboxy-
diimides 2.10 Such liquid crystalline dyes show important
functional properties (e.g. photoconductivity) originating from
the combination of liquid crystallinity and absorption in the
visible region.11
We recently reported the synthesis of coronenetetracarboxy-
diimides 9,12 which were prepared in a few steps from
perylenetetracarboxydiimides 2 in high yields. The new dyes
9 constituted further examples of chromophores with liquid
crystalline properties like the above mentioned perylene
derivatives 2, 7 and 8. Based on the readily available and
extremely robust perylenediimide chromophore, the aim of this
research work was to provide new liquid crystalline derivatives
with different spectral properties. Therefore we proceeded to
investigate the coronenediimides 9 and also tried to synthesize
further coronene derivatives such as the coronenemonoimide
10. We present here our synthetic work towards the
coroneneimides in detail and give some of the physical data
such as X-ray diffraction spectra and charge carrier mobilities.
As we were interested in the new yellow chromophores 9 and
wanted to investigate these coronene derivatives with respect to
their chromophoric and possible liquid crystalline properties,
we searched for a route to synthesize 9 in a more selective way.
First of all, one had to prevent the nucleophilic attack of
piperidine in the bay-region of the perylenediimides 13. The use
of a tertiary nitrogen base such as triethylamine or a sterically
hindered piperidine derivative as the base in the Hagihara
coupling proved to be successful. As shown in Scheme 3
the products of the palladium catalyzed reaction of 13 with an
alkyne in this case were the bisalkynyl substituted perylene-
diimides 14, and only very small amounts (v5%) of the
coronenediimides 9 were isolated. The products 14 were
characterized by NMR and UV/Vis spectroscopy, FD mass
spectrometry and elemental analysis. In the 1H NMR the
presence of two isomers of 14 (N,N’-dialkyl-1,7-dialkynyl-
perylene-3,4:9,10-tetracarboxydiimide and N,N’-dialkyl-1,
6-dialkynylperylene-3,4:9,10-tetracarboxydiimide) could be
observed. Integration of the signals showed that the ratio of
the two isomers is 94% : 6%. Due to the symmetry of both
isomers, an assignment of the signals to the individual isomers
was not possible. Each dibromoperylenediimide 13 is known to
consist of two isomers as well, but for 13 the separate
integration of the characteristic signals proved to be impos-
sible. We believe that in the bromination of 11 the 1,7-isomer of
12 is the preferred product and as 13 arises from 12 by just
substituting the bromine atoms, the 1,7-dialkynyl substituted
perylenediimides should be the major products as well. There is
no way of separating the isomers of 13 or 14 on a larger scale,
so the isomeric mixtures were used as such.14
Results and discussion
The next step in the synthesis of the coronenediimides 9 was
the controlled cyclization of 14. Several reaction conditions for
initiating the cyclization were tested. The presence of a base
seemed to be necessary, but the use of potassium hydroxide or
tert-butoxide caused saponification of the imide function of 14.
Finally, the use of the strong, but non-nucleophilic base
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) resulted in a color
change from red to yellow as expected for the formation of 9.
FD-mass spectrometry as well as NMR and UV/Vis spectro-
scopy proved that 9 had been formed. Similar to the case of 13
The whole story started with a surprise (see Scheme 2): the
N,N’-dicyclohexyl-1,7-dibromoperylene-3,4:9,10-tetracarboxy-
diimide 13a was treated with dodec-1-yne employing the
reaction conditions used for the functionalization of 3,9(10)-
dibromoperylene or 9-bromoperylene-3,4-dicarboximides;13
thereby, piperidine, the base used in the palladium catalyzed
reaction, acted as a nucleophile, thus substituting the bromine
atoms in the bay-region of the perylene derivative 13a to give
the isolated products 15 and 16 and a third reaction product, a
DOI: 10.1039/b009708j
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Scheme 1 Important dyes with perylene and coronene units.
1
and 14, the aromatic region of the H-NMR spectrum shows
the presence of two isomers of 9. In the UV/Vis spectra of 14d
(Fig. 1a) an absorption band at 552 nm with the typical
perylene fine structure can be observed. The coronene
derivative 14d does not absorb in that region, but shows
three absorption bands in the visible – a weak band at 511 nm
and stronger bands at 338 and 428 nm which give rise to yellow
color. The absorption bands at 511 and 428 nm show the
typical perylene vibrational structure while the short wave-
length absorption at 338 nm does not.15
derivatives, having short alkyl chains at the coronene core
(9b, 9d) or bulky N-substituents (9g), the formation of a
mesophase could not be observed.
The accurate identification of the mesophases was performed
by X-ray diffraction. The characteristic signals for a columnar
discotic mesophase (Colho) formed by the liquid crystalline
derivatives of 9 can be seen in Fig. 3.
The alkyl chains give rise to the reflexion at 2h~17.6u (halo
reflexion). The (001) reflexion can be seen at 2h~25u, corres-
˚
ponding to an intracolumnar distance of 3.6 A. From the very
strong (100) reflexion at 2h~4.4u the intercolumnar distance of
Various derivatives of 9 were synthezised following the route
described above (Scheme 3). During these experiments, a severe
limitation of the cyclization reaction was observed in that
sterically demanding substituents such as tert-butyl (14c) or
phenyl (14i) next to the triple bond of 14 prevented the
formation of the corresponding coronenediimide 9.
Disc shaped molecules such as the above mentioned perylene
derivatives 7 and 8 having an extended planar p-system and
mobile alkyl chains often show liquid crystalline behaviour.9
The coronenediimides 9 were therefore investigated with regard
to mesophase formation.
First of all, DSC traces of the substances 9 were monitored.
Fig. 2 shows a typical example (9e): At 191 uC a phase
transition can be observed. Polarizing microscopy proved
that this corresponds to the transition into the mesophase, as
characteristic textures could be observed for 9e for tempera-
tures above 191 uC. Table 1 summarizes the transition temp-
eratures for the different derivatives of 9. For some
˚
about 20 A can be calculated. The hexagonal order of the
columns is proved by the weak (110) reflexion at 2h~7.7u.
Similar diffraction patterns were obtained for all other liquid
crystalline coronenediimides 9. The optical behaviour of 9 in
polymer films resulting from the formation of aggregates
depending on the concentration of 9 in those films was
discussed in an earlier publication.12
One major disadvantage for possible applications of the
liquid crystals 9 is their very high temperatures for transition
into the mesophase (between 177 and 266 uC). The variation of
the alkyl chains at the coronene core or the imide nitrogen
atom gave a decrease in the melting temperature of about 90 uC
(from 266 (9d) to 177 uC (9f)). But even a melting temperature
of 177 uC is much too high for investigations such as
measurements of charge carrier mobilities in the mesophase.
Another way of influencing the melting temperature is
the variation of the chromophore itself. Therefore the
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Scheme 2 Reaction products of the Hagihara coupling in the bay region of N,N’-dicyclohexyl-1,7-dibromoperylene-3,4:9,10-tetracarboxydiimide
(13a): a: dodec-1-yne, THF–piperidine (1 : 1), 8 mol% [Pd(PPh3)4], 10 mol% CuI, 60 uC, 4 h.
tribromoperylenemonoimide 18 was subjected to the same
reaction conditions like the earlier described dibromoperylene-
diimides 13 (Scheme 4).
the spectrum of the coronenemonoimide 10 except that
positions of the bands are shifted to lower wavelengths.
As in the case of the coronenediimides 9, the coronene-
monoimide 10 was first investigated by DSC which showed a
phase transition at 160 uC (Fig. 5). Polarizing microscopy then
revealed that this is the transition from the mesophase to the
isotropic melt, as one could see characteristic structures for
temperatures below 160 uC, and for temperatures over 160 uC
the image turned black. This means that compound 10 is liquid
crystalline at room temperature and that the transition
temperature into the mesophase must be below 0 uC, which
is significantly lower than for the coronenediimides 9. X-Ray-
diffraction of compound 10 also showed the characteristic
peaks of a columnar mesophase (Colho), the reflexions are
summarized in Table 2. In addition X-ray diffractograms of
compounds 19 (Ti~135 uC) and 20 (Ti~269 uC) were mea-
sured and their reflexions, which were characteristic for a
columnar mesophase are presented in Table 2.
The synthesis of coronenemonoimide 10 thus yielded a
substance showing a columnar discotic mesophase at room
temperature. This made an investigation of the charge carrier
mobility in the mesophase possible.
The one-dimensional, intracolumnar charge carrier mobility
for compound 10, measured using the pulse-radiolysis time-
resolved microwave conductivity technique (PR-TRMC), is
shown as a function of temperature in Fig. 6. The value of Sm1D
is close to 0.2 cm2 Vs21 at room temperature. The mobility
increases gradually with increasing temperature up to a value
of ca. 0.3 cm2 Vs21 just below 160 uC at which a transition to
the isotropic liquid phase was proposed to occur. At this
temperature an abrupt decrease of approximately 20% occurs.
N-(2,6-Diisopropylphenyl)-1,6,9-tribromoperylene -3,4-di-
carboximide (18) was synthesized from N-(2,6-diisopropyl-
phenyl)perylene-3,4-dicarboximide (17)16 by treating 17 with
elemental bromine. Minor amounts of tetrabromoperylene-
monoimide were present as an impurity in the crude material
and could be separated by column chromatography. Hagihara
coupling of 18 with dodec-1-yne was performed as described
above, but lower reaction temperatures were employed as the
reaction occurred much faster than for the dibromoperylene-
diimides 13. It is worth mentioning, that (in contrast to the
dialkynyl substituted perylenediimides 14) only one isomer of
19 was isolated, as could be proved by NMR spectroscopy. The
bromination of 17 works regioselectivly and only the 1,6,9-
tribromoperylene-3,4-dicarboximide 18 was obtained. In the
aryl–alkyne coupling the alkyne substituents are exchanged for
the bromine atoms, resulting selectively in the 1,6,9-trialk-
ynylperylene-3,4-dicarboximide 19. Compound 19 is a dark red
substance with an absorption in chloroform solution at
549 nm, and a fluorescence maximum at 571 nm (Stokes shift
19 nm). When 19 was subjected to the reaction conditions of
the base induced cyclization, the triple bond in the 9-position of
the perylenemonoimide 19 was not affected and the coronene-
monoimide derivative 20, still containing a triple bond, was
isolated. The triple bond was then hydrogenated13 with
elemental hydrogen in the presence of palladium on charcoal
to give product 10. Fig. 4 shows the UV/Vis spectra of
coronenediimide 9c (Fig. 4a) and coronenemonoimide 10
(Fig. 4b). The same absorption bands as for 9 can be seen in
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Scheme 3 Synthesis of coronenediimides 9: a: Br2, 100% H2SO4, 40 uC, 12 h, 90–95%; b: R1NH2, CH3COOH, NMP, 85 uC, 8 h, 88–95%; c:
R2CMCH, 8 mol% [Pd(PPh3)4], 10 mol% CuI, THF–Et3N (1 : 1), 80 uC, 14 h, 85–95%; d: DBU, toluene, 100 uC, 12 h, 95–100%. (NMP~N-
methylpyrrolidone; DBU~1,8-diazabicyclo[5.4.0]undec-7-ene.)
This decrease is much smaller than has been previously found
at the mesophase to isotropic liquid phase transition for other
discotic materials.17 We conclude that the ‘‘isotropic’’ phase of
Conclusion
The mobility values found for 10 are a factor of 2 larger than
that found by time-of-flight (TOF) and PR-TRMC measure-
ments for the helical mesophase of hexakis(hexylthio)triphe-
nylene17d and close to the record mobility value recently
reported for a liquid crystalline derivative of hexabenzo-
coronene.18 The values are also similar to those previously found
10 still retains a high degree of columnar order and may in fact
be more correctly considered to be a highly fluid mesophase
rather than an isotropic liquid.
Fig. 1 UV/Vis-spectra of a) 14d (CHCl3); b) 9c (CHCl3).
Fig. 2 DSC trace of 9e (10 K min21).
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Fig. 3 X-Ray diffraction of 9e at 200 uC.
Fig. 4 UV/Vis spectra of a) coronenediimide 9c; b) coronenemono-
imide 10.
Table 1 Melting points of coronenediimide derivatives 9
for the imido derivatives of perylene 7 and 8.19 Imido
substituted aromatic compounds are of interest for practical
applications because they have been shown to have n-type, i.e.
electron conducting, semiconductive characteristics20 in con-
trast to the more usual p-type, hole transport, behaviour of
other discotic materials. The coronenemonoimide derivative
studied in the present work is of particular interest because of
its liquid crystalline properties even at room temperature and
the fact that it has a readily accessible fluid phase which makes
possible the ready processing of thin film device structures.
R2
R1~C6H11
R1~C8H17
R1~diisopropylphenyl
C6H13
9a
w350a
—
—
9e
—
—
9g
CH(CH3)C3H7 9b
w350a
9c
C10H21
Cr 245 Colho Cr 192 Colho Cr 277 I
9d 9f
Cr 266 Colho Cr 177 Colho
aMesophase could not be observed.
C
13H27
—
Scheme 4 Synthesis of coronenemonoimide 10: a: Br2, CHCl3, reflux, 6 h, 86%; b: R1CMCH, 8 mol% [Pd(PPh3)4], 10 mol% CuI, THF–Et3N (1 : 1),
60 uC, 12 h, 80%; c: DBU, toluene, 100 uC, 24 h, 65%; d: H2, Pd-C, THF, 22 uC, 1 h, 90%.
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Table 2 X-Ray diffraction peaks of a) 10 at 110 uC; b) 19 at 97 uC; c) 20
at 127 uC
10
2h~
19
20
Reflexion
(100)
(110)
(001)
Halo
4.60
7.96
24.20
18
4.42
4.46
7.72
25.00
—
24.86
15–22
15–22
Experimental section
Equipment and materials
NMR spectra were recorded on Bruker DPX 250, Bruker
AMX 300 and Bruker 500 DRX spectrometers (at room
temperature, unless otherwise noted); the operating frequencies
are given with the data. FD mass spectra were recorded on a
VG instruments ZAB2-SE-FPD. IR-spectra (KBr method)
were recorded on a Nicolet FT-IR 320 spectrometer. UV/Vis
spectra were recorded on a Perkin–Elmer Lambda 9 spectro-
meter, and fluorescence spectra were measured on a Spex
Fluorolog 2 Type F 212 spectrometer. Column chromato-
graphy was performed on silica gel (Merck, Geduran Si60),
mesh size 70–230. Thermogravimetric analyses were performed
on a Mettler TG 50 thermobalance. Elemental analyses were
performed by the Department of Chemistry and Pharmacy of
the University, Mainz.
Fig. 6 Charge carrier mobility of 10 as a function of temperature
(measured by pulse-radiolysis time resolved microwave conductivity
technique (PR-TRMC)).
organised columnar domains within the present bulk samples
are randomly orientated and that charge transport is expected
to be highly anisotropic and to occur almost exclusively along
the axis of the macrocyclic stacks. The mobility sum,
Sm1D~m(z)zm(2), is used in eqn. (1) since the PR-TRMC
technique does not allow the determination of the separate
contributions of the positive and negative charge carriers to the
radiation-induced conductivity.
All comercially available reagents and solvents were used
without further purification unless otherwise stated. THF was
distilled from potassium. Hydrogen gas was purchased from
Linde and used without further purification.
Synthesis of N,N’-dialkyl-1,7-dibromoperylene-3,4:9,10-
tetracarboxydiimides 13 (procedure A)
A
mixture of 1,7-dibromoperylene-3,4:9,10-tetracarboxylic
dianhydride (12) (10 g; 18 mmol) and NMP (450 ml) were
heated to 85 uC. Glacial acetic acid (6.2 g; 0.1 mol) and the
amine (55 mmol) were added slowly. After stirring at 85 uC for
12 h the mixture was cooled to room temperature and the
product was isolated by filtration and washed with methanol.
Measurement of charge transport properties
The charge transport properties of coronenemonoimide 10
were investigated using the pulse-radiolysis time-resolved
microwave conductivity technique (PR-TRMC). In brief, a
uniform, micromolar concentration of charge carriers is
formed in the material by a nanosecond pulse of ionizing
radiation (3 MeV electrons from a Van de Graaff accelerator).
Microwaves (26–38 GHz) are used to quantitatively probe
(without the need of electrode contacts) the radiation-induced
conductivity within the sample. The precise experimental
methodology and data reduction procedures have been
reported previously.17b–d,21
N,N’-Dicyclohexyl-1,7-dibromoperylene-3,4:9,10-tetracarboxy-
diimide (13a). 1,7-Dibromoperylene-3,4:9,10-tetracarboxylic
dianhydride (12) (10 g; 18 mmol) and cyclohexylamine
(5.34 g; 54 mmol) were reacted as described in procedure A
to yield the red compound (13a) (10.25 g; 80%). Mpw250 uC;
3
1H NMR (500 MHz, CD2Cl2): d~9.47 (d, J (H,H)~8 Hz, 2
H; H-6, H-12), 8.86 (s, 2 H; H-2, H-8), 8.63 (d, 3J (H,H)~8 Hz;
2 H; H-5, H-11), 5.00 (m, 2 H; 2 N-CH), 2.53 (m, 4 H; 4
CHcyclohex), 1.91 (m, 4 H; 4 CHcyclohex), 1.75 (m, 6 H; 6
CHcyclohex), 1.47 (m, 4 H; 4 CHcyclohex), 1.34 (m, 2 H; 2
CHcyclohex); 13C NMR (125 MHz, CD2Cl2): d~163.65 (CLO),
163.10 (CLO), 138.22, 138.07, 133.20, 133.02, 130.08, 129.63,
128.87, 128.49, 127.40, 124.24, 123.82, 121.02, 54.59, 30.10,
29.50, 26.98, 25.92; UV/Vis (CHCl3): lmax (e)~526 (57300),
490 (40000), 459 (14970), 390 (6800), 272 (30200), 264 nm
(28950 l mol21 cm21); fluorescence emission (CHCl3, exc.:
526 nm): lem~547 nm; MS (8 kV; FD): m/z~710.8 (100%)
[Mz] (calcd. 710.04); IR (KBr): (cm21)~2930, 2926, 2851,
1700, 1698, 1659, 1588, 1452, 1419, 1398, 1361, 1327, 1301,
1257, 1239, 1166, 1156, 1143, 1115, 984, 979, 659, 630, 624, 806,
691, 603.
The one-dimensional, intracolumnar charge carrier mobility
was determined from the end-of-pulse conductivity per unit
dose, Dseop/D (Sm2 J21), using the relationship
Dseop Ep
.
Sm1D ~ 3
(1)
D
Wp
In eqn. (1) Ep (eV) is the average energy per initial ionization
event and Wp is the probability that ion-pairs survive to the end
of the pulse. Using the model described previously17c,21 values
of 25 and 0.37 eV were used for Ep and Wp respectively. The
factor of 3 in eqn. (1) takes into account the fact that the
N,N’-Di(n-octyl)-1,7-dibromoperylene-3,4:9,10-tetracarboxy-
diimide (13b). 1,7-Dibromoperylene-3,4:9,10-tetracarboxylic
dianhydride (12) (10 g, 18 mmol) and n-octylamine (7.1 g,
54 mmol) were reacted as described in procedure A to yield the
red compound (13b) (11.4 g; 82%). Mpw250 uC; 1H NMR
(500 MHz, CD2Cl2): d~9.29 (d, 3J (H,H)~8 Hz, 2 H; H-6,
3
H-12), 8.72 (s, 2 H; H-2, H-8), 8.50 (d, J (H,H)~8 Hz, 2 H;
H-5, H-11), 4.12 (t, 3J (H,H)~7 Hz, 4 H; 2 N-CH2), 1.70 (m, 4 H;
2 CH2), 1.41–1.23 (m, 20 H; 10 CH2), 0.87 (t, 3J (H,H)~7 Hz, 6
H; 2 CH3); 13C NMR (75 MHz, CD2Cl2): d~162.70, 162.18,
Fig. 5 DSC-trace of 10 (10 K min21).
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H, 12 CHpiperidine and 16 CHcyclohex); UV/Vis (CHCl3): lmax
137.83, 137.72, 132.68, 132.53, 129.64, 129.04, 128.41, 126.81,
123.24, 122.79, 120.74, 40.78, 31.94, 29.42, 29.34, 28.10, 27.24,
22.75, 13.94. UV/Vis (CHCl3): lmax (e)~526 (56590), 490
(38200), 459 (15040), 390 (6640), 272 (30130), 264 nm
(29190 l mol21 cm21); fluorescence emission (CHCl3, exc.:
526 nm): lem~547 nm; MS (8 kV, FD): m/z~770.0 (100%)
[Mz] (calcd. 770.13); C40H40Br2N2O4 (772.57): calcd.: C 62.19,
H 5.22, Br 20.69, N 3.63, O 8.28%; found C 61.77, H 5.31, Br
20.64, N 3.54%.
(e)~675
(broad)
(10385),
445
(10232),
280 nm
(20501 l mol21 cm21); MS (8 kV, FD): m/z~720.50 (100%)
[Mz] (calcd. 720.37).
Reaction of N,N’-dialkyl-1,7-dialkynylperylene-3,4:9,10-
tetracarboxydiimides 14 with alkynes in the presence of
triethylamine (Scheme 3)
Dibromoperylene 13 (3 mmol) was dissolved in a mixture of
dry THF (250 ml) and dry triethylamine (250 ml) in an argon
atmosphere. Pd(PPh3)4 (347 mg, 0.3 mmol) and CuI (46 mg,
0.24 mmol) were added under argon atmosphere. The alkyne
(12 mmol, 4 equivalents) was added with a syringe through a
septum. After stirring at 80 uC for 12 h the mixture was poured
into the same amount of cold dilute HCl (HCl : H2O~1 : 3) and
the product was extracted with dichloromethane. The organic
layer was extracted with water until the aqueous layer was
neutral. The crude product was purified by column chromato-
graphy on silica gel (CH2Cl2).
N,N’-Bis(2,6-diisopropylphenyl)-1,7-dibromoperylene-3,4:9,10-
tetracarboxydiimide 13c (procedure B)
1,7-Dibromoperylene-3,4:9,10-tetracarboxylic dianhydride (12)
(12 g, 22 mmol) and 2,6-diisopropylaniline (17.73 g, 0.1 mol)
were heated to 160 uC in propionic acid (280 ml). After stirring
in an argon atmosphere at this temperature for 16 h the warm
solution was filtered. The product precipitated after addition of
water to the filtrate and was isolated by filtration. The crude
product was washed with water until neutral and dried in vacuo
over P2O5 to give the diimide (13c) (15 g, 78%). Mpw250 uC;
1H NMR (250 MHz, CD2Cl2): d~9.60 (d, 3J (H,H)~8 Hz,
2 H; H-6, H-12), 9.01 (s, 2 H; H-2, H-8), 8.78 (d, 3J
(H,H)~8 Hz, 2 H; H-5, H-11), 7.54 (t, 3J (H,H)~8 Hz,
2 H), 7.38 (d, 3J (H,H)~8 Hz, 4 H), 2.75 (septet, 3J
(H,H)~7 Hz, 4 H; 4 CHisopropyl), 1.15 (d, 3J (H,H)~7 Hz,
12 H; 4 (CH3)isopropyl); 13C NMR (125 MHz, CD2Cl2):
d~163.51, 163.04, 146.42, 138.85, 138.74, 133.93, 133.70,
131.07, 130.86, 130.72, 130.08, 130.02, 129.22, 128.82, 128.11,
124.54, 123.61, 123.21, 121.39, 29.61, 24.10; UV/Vis (CHCl3):
lmax (e)~527 (53100), 491 (36380), 459 (14570), 390 (6350),
260 nm (32120 l mol21 cm21); fluorescence emission (CHCl3,
exc.: 526 nm): lem~547 nm; MS (8 kV, FD): m/z~868.5
(100%) [Mz] (calcd. 866.13).
N,N’-Dicyclohexyl-1,7-di(dodec-1-ynyl)perylene-3,4:9,10-tetra-
carboxydiimide
(14a). N,N’-Dicyclohexyl-1,7-dibromopery-
lene-3,4:9,10-tetracarboxydiimide (13a) (3 g, 4.2 mmol) and
dodec-1-yne (2.6 g, 15.6 mmol) were reacted as described for
(14) to yield (14a) (3.3 g, 89%). Mp 175 uC; 1H NMR
(500 MHz, CDCl3): d~9.98 (d, 3J (H,H)~8 Hz, 2 H; H-6,
3
H-12), 8.62 (s, 2 H; H-2, H-8), 8.50 (d, J (H,H)~8 Hz, 2 H;
H-5, H-11), 5.00 (tt, 3J1 (H,H)~12 Hz, 3J2 (H,H)~4 Hz, 2 H;
2 N-CH), 2.62 (t, 3J (H,H)~7 Hz, 4 H; 2 MCH2), 2.57 (m, 4 H;
4 CHcyclohex), 1.92 (m, 8 H; 4 CHcyclohex, 2 CH2), 1.75 (m, 10 H;
6 CHcyclohex, 2 CH2), 1.55–1.24 (m, 30 H; 12 CH2 und
6 CHcyclohex), 0.86 (t, 3J (H,H)~7 Hz; 6 H, 2 CH3). 13C NMR
(125 MHz, CDCl3): d~163.53 (CLO), 163.28 (CLO), 137.84,
133.64, 133.17, 129.84, 127.09, 127.06, 126.51, 123.18, 122.21,
120.56, 101.67 (CMC), 82.40 (CMC), 54.02 (CH-N), 31.92, 29.64,
29.34, 29.27, 29.25, 29.11, 28.32, 26.59, 25.48, 22.68, 20.30,
14.09 (CH3); UV/Vis (CHCl3): lmax (e)~552 (45870), 511
(28300), 476 (14800), 297 nm (41720 l mol21 cm21); fluores-
cence emission (CHCl3, exc.: 552 nm): lem~571 nm; MS (8 kV,
FD): m/z~882.3 (100%) [Mz] (calcd. 882.53); C60H70N2O4
(883.22): calcd. C 81.59, H 7.99, N 3.17, O 7.25%; found C
81.19, H 8.02, N 3.04%.
Reaction of N,N’-dicyclohexyl-1,7-dibromoperylene-3,4:9,10-
tetracarboxydiimide (13a) with dodec-1-yne in the presence of
piperidine (Scheme 2)
N,N’-Dicyclohexyl-1,7-dibromoperylene-3,4:9,10-tetracarboxy-
diimide (13a) (500 mg, 0.7 mmol) was dissolved in a mixture of
dry THF (150 ml) and dry triethylamine (150 ml) in an argon
atmosphere. Pd(PPh3)4 (32 mg, 0.03 mmol) and CuI (6.5 mg,
0.02 mmol)were added under argon atmosphere. Dodec-1-yne
(466 mg, 2.8 mmol) was added with a syringe through a
septum. After stirring at 80 uC for 12 h the mixture was poured
into the same amount of diluted cold HCl (HCl : H2O~1 : 3)
and the product was extracted with dichloromethane. The
organic layer was extracted with water until the aqueous layer
was neutral. The crude reaction mixture was seperated by
column chromatography on silica gel (CH2Cl2). The products
9a (23%), 15 (28%) and 16 (34%) were isolated (percentages
after column chromatography). Analytical data for 9a see
below. Analytical data for 15 (major isomer): 1H NMR
(500 MHz, CD2Cl2): d~10.56 (d, 3J (H,H)~9 Hz, 1 H;
aromatic H), 9.27 (s, 1 H; aromatic H), 9.09 (s, 1 H; aromatic
H), 8.78 (d, 3J (H,H)~9 Hz, 1 H; aromatic H), 8.72 (d, 3J
(H,H)~9 Hz, 1 H; aromatic H), 8.28 (d, 3J (H,H)~9 Hz, 1 H;
aromatic H), 5.17 (m, 2 H, 2 N-CHcyclohex), 3.45 (m, 4 H,
2 CH2-Npiperidine), 2.83–2.65 (m, 6 H; MCH2, 2 CH2CH2-
Npiperidine), 1.99–1.75 (m, 18 H; 9 CH2), 1.55–1.25 (m, 20 H;
10 CH2), 0.85 (t, 3J (H,H)~7 Hz, 3 H, CH3). UV/Vis
(dioxane): lmax (e)~528 (15060), 463 (20130), 282 nm
(30052 l mol21 cm21); MS (8 kV, FD): m/z~802.00 (100%)
[Mz] (calcd. 801.45); Analytical data for 16: 1H NMR
(250 MHz, CD2Cl2): d~9.60 (d, 3J (H,H)~9 Hz, 2 H;
N,N’-Dicyclohexyl-1,7-bis(3-methylhex-1-ynyl)perylene-
3,4:9,10-tetracarboxydiimide
(14b). N,N’-Dicyclohexyl-1,
7-dibromoperylene-3,4:9,10-tetracarboxydiimide (13a) (1 g,
1.4 mmol) and 3-methylhex-1-yne (405 mg, 4.22 mmol) were
reacted as described for (14) to yield 14b (950 mg, 91%).
1
3
Mpw250 uC; H NMR (500 MHz, CD2Cl2): d~10.13 (d, J
(H,H)~8 Hz, 2 H; H-6, H-12), 8.65 (s, 2 H; H-2, H-8), 8.55
(d, 3J (H,H)~8 Hz, 2 H; H-5, H-11), 4.99 (m, 2 H; 2 N-CH),
2.92 (m, 2 H; 2 CH), 2.54 (m, 4 H; 4 CHcyclohex), 1.91 (m, 4 H;
4 CHcyclohex), 1.76–1.43 (m, 20 H; 12 CHcyclohex and 4 CH2),
1.41 (d, 3J (H,H)~6.7 Hz, 6 H; 2 CH3), 1.01 (t, 3J
(H,H)~7 Hz, 6 H; 2 CH3); 13C NMR (125 MHz, CDCl3):
d~163.52, 163.34, 137.83, 133.82, 133.34, 129.85, 127.20,
127.03, 126.78, 123.01, 122.05, 120.70, 105.57, 82.31, 53.88,
38.42, 28.93, 26.97, 26.38, 25.28, 20.67, 20.30, 13.88; UV/Vis
(CHCl3): lmax (e)~552 (47320), 511 (27990), 476 (15030),
297 nm (41870 l mol21 cm21); fluorescence emission (CHCl3,
exc.: 552 nm): lem~571 nm; MS (8 kV, FD): m/z~742.4
(100%) [Mz] (calcd. 742.37).
N,N’-Dicyclohexyl-1,7-bis(3,3-dimethylbut-1-ynyl)perylene-3,
4:9,10-tetracarboxydiimide
(14c). N,N’-Dicyclohexyl-1,
aromatic H), 8.44 (s,
2
H; aromatic H), 8.37 (d, 3J
7-dibromoperylene-3,4:9,10-tetracarboxydiimide (13a) (500 mg,
0.7 mmol) and tert-butylethyne (230 mg, 2.8 mmol) were reacted
as described for (14) (reaction temperature 50uC) and the red
product (14c) was isolated (463 mg, 92%). Mp 217 uC; 1H
(H,H)~9 Hz, 2 H; aromatic H), 5.00 (m, 2 H, 2 N-CHcyclohex),
3.55–3.38 (m, 4 H, 4 CHpiperidine), 3.05–2.86 (m, 4 H, 4
CHpiperidine), 3.73–2.48 (m, 4 H, 4 CHcyclohex), 2.08–1.25 (m, 28
J. Mater. Chem., 2001, 11, 1789–1799
1795

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2959, 2926, 2868, 2853, 1711, 1670, 1622, 1595, 1467, 1456,
1406, 1384, 1362, 1336, 1241, 912, 740; C64H82N2O4 (943.36):
calcd. C 81.49, H 8.76, N 2.97, O 6.78%; found C 79.93, H 8.73,
N 2.85%.
NMR (500 MHz, C2DCl3): d~10.09 (d, 3J (H,H)~8 Hz,
2 H; H-6, H-12), 8.68 (s, 2 H; H-2, H-8), 8.58 (d, 3J
(H,H)~8 Hz, 2 H; H-5, H-11), 5.01 (m, 2 H; 2 CH-N), 2.55
(m, 4 H; 4 CHcyclohex), 1.91 (m, 4 H; 4 CHcyclohex), 1.74
(m, 6 H; 6 CHcyclohex), 1.45 (m, 22 H; 4 CHcyclohex, 6 CH3),
1.32 (m, 2 H; 2 CHcyclohex); 13C NMR (125 MHz, C2D2Cl4,
50 uC): d~164.02, 163.83, 138.19, 134.39, 133.89, 130.25, 127.79,
127.59, 127.27, 123.64, 122.64, 121.22, 109.29, 81.48, 54.48,
34.90, 30.72, 29.93, 29.48, 29.18, 29.90, 25.80; UV/Vis (CHCl3):
lmax (e)~552 (45680), 511 (27020), 476 (14960), 297 nm
(41310 l mol21 cm21); fluorescence emission (CHCl3, exc.:
552 nm): lem~571 nm; MS (8 kV, FD): m/z~715.2 (100%)
[Mz] (calcd. 714.34).
N,N’-Di(n-octyl)-1,7-di(pentadec-1-ynyl)perylene-3,4:9,10-
tetracarboxydiimide (14g). N,N’-Di(n-octyl)-1,7-dibromopery-
lene-3,4:9,10-tetracarboxydiimide (13b) (3 g, 3.8 mmol) and
pentadec-1-yne (3.2 g, 15.5 mmol) were reacted as described
for (14). The red product (14g) (3.5 g, 89%) was isolated.
Mp 152 uC; 1H NMR (500 MHz, CD2Cl2): d~9.33 (d, 3J
(H,H)~8 Hz, 2 H; H-6, H-12), 8.03 (s, 2 H; H-2, H-8), 7.85 (d, 3J
(H,H)~8 Hz, 2 H; H-5, H-11), 4.07 (m, 8 H; 2 CH2-N, 2 CH2M),
1.95–1.18 (m, 68 H; 34 CH2), 0.90 (m, 12 H; 4 CH3); 13C NMR
(125 MHz, CD2Cl2): d~163.02, 162.87, 138.03, 134.12, 132.93,
129.93, 129.13, 128.73, 128.52, 127.08, 127.01, 126.98, 126.63,
122.97, 122.58, 122.03, 121.72, 120.80, 120.53, 103.83, 83.03,
41.31, 41.08, 32.84, 32.41, 30.28, 30.25, 30.19, 30.13, 30.09, 29.95,
29.90, 29.83, 29.75, 28.83, 27.72, 23.21, 23.15, 20.77, 14.34, 14.28;
UV/Vis (CHCl3): lmax (e)~552 (46580), 511 (29130), 476 (15240),
297 nm (40980 l mol21 cm21); fluorescence emission (CHCl3,
exc.: 552 nm): lem~572 nm; MS (8 kV, FD): m/z~1026.7
(100%) [Mz], 2054.3 (70%) [M2z], 3081.4 (20%) [M3z] (calcd.
1027.7).
N,N’-Dicyclohexyl-1,7-di(oct-1-ynyl)perylene-3,4:9,10-tetra-
carboxydiimide
(14d). N,N’-Dicyclohexyl-1,7-dibromopery-
lene-3,4:9,10-tetracarboxydiimide (13a) (750 mg, 1 mmol) and
oct-1-yne (467 mg, 4 mmol) were reacted as described for (14)
to give the red product 14d (750 mg, 92%). Mp 221 uC; 1H
3
NMR (500 MHz, CD2Cl2): d~9.03 (d, J (H,H)~8 Hz, 2 H;
3
H-6, H-12), 7.85 (s, 2 H; H-2, H-8), 7.73 (d, J (H,H)~8 Hz,
2 H; H-5, H-11), 4.91 (m, 2 H; 2 N-CH), 2.58 (m, 6 H; 2 MCH2,
4 CHcyclohex), 2.00 (m, 8 H; 4 CHcyclohex, 2 CH2), 1.78 (m, 10 H;
6 CHcyclohex, 2 CH2), 1.48 (m, 14 H; 4 CH2 und 6 CHcyclohex),
1.00 (t, 3J (H,H)~7 Hz, 6 H; 2 CH3); 13C NMR (75 MHz,
C2D2Cl4): d~163.12, 162.91, 137.46, 133.03, 132.47, 129.45,
126.53, 126.39, 125.96, 122.65, 121.70, 120.11, 101.97, 81.95,
53.82, 31.15, 28.73, 28.04, 26.41, 22.42, 20.04, 13.99; UV/Vis
(CHCl3): lmax (e)~552 (46210), 511 (28900), 476 (15050),
297 nm (41320 l mol21 cm21); fluorescence emission (CHCl3,
exc.: 552 nm): lem~571 nm; MS (8 kV, FD): m/z~770.3
(100%) [Mz] (calcd. 770.41).
N,N’-Bis(2,6-diisopropylphenyl)-1,7-di(dodec-1-ynyl)perylene-
3,4:9,10-tetracarboxydiimide
(14h). N,N’-Bis(2,6-diisopropyl-
phenyl)-1,7-dibromoperylene-3,4:9,10-tetracarboxydiimide (13c)
(3 g, 3.46 mmol) and dodec-1-yne (1.72 g, 10.38 mmol)
were reacted as described for (14) to give the product (14h)
(3,1 g, 85%). Mp 191 uC; 1H NMR (500 MHz, CD2Cl2): d~10.25
(d, 3J (H,H)~8 Hz, 2 H; H-6, H-12), 8.84 (s, 2 H; H-2, H-8), 8.74
(d, 3J (H,H)~8 Hz, 2 H; H-5, H-11), 7.57 (t, 3J (H,H)~8 Hz, 2 H),
7.43 (d, 3J (H,H)~8 Hz, 4 H), 2.75 (septet, 3J (H,H)~7 Hz, 4 H;
4 CHisopropyl), 2.68 (t, 3J (H,H)~7.3 Hz, 4 H; 2 CH2M), 1.94 (m, 4 H;
2 CH2), 1.78 (m, 4 H; 2 CH2), 1.61–1.19 (m, 24 H; 12 CH2), 1.17 (d,
3J (H,H)~7 Hz, 12 H; 4 (CH3)isopropyl), 0.83 (t, 3J (H,H)~7 Hz, 6
H; 2 CH3); 13C NMR (125 MHz, CD2Cl2): d~164.21, 163.79,
146.31, 146.27, 142.37, 138.47, 136.93, 133.97, 131.40, 131.29,
130.80, 130.58, 129.71, 129.45, 128.47, 126.62, 125.72, 124.27,
124.21, 123.05, 122.39, 122.14, 121.62, 121.14, 103.30, 83.07, 31.99,
29.69, 29.64, 29.60, 29.48, 29.40, 29.37, 29.34, 28.60, 23.90, 23.82,
22.74, 20.58, 13.93; UV/Vis (CHCl3): lmax (e)~552 (46980),
511 (27790), 476 (14980), 297 nm (40329 l mol21 cm21); fluores-
cence emission (CHCl3, exc.: 552 nm): lem~572 nm; MS (8 kV,
FD): m/z~1039.2 (100%) [Mz] (calcd. 1038.63); C72H82N2O4
(1069.52): calcd. C 83.10, H 8.29, N 2.62, O 5.98%; found C 82.79, H
8.22, N 2.56%.
N,N’-Dicyclohexyl-1,7-di(pentadec-1-ynyl)perylene-3,4:9,10-
tetracarboxydiimide (14e). N,N’-Dicyclohexyl-1,7-dibromopery-
lene-3,4:9,10-tetracarboxydiimide (13a) (1 g, 1.4 mmol) and
pentadecyne (880 mg, 4.23 mmol) were reacted as described for
(14) and the red product (14e) (1.1 g, 81%) was isolated. Mp
164 uC; 1H NMR (300 MHz, CD2Cl2): d~9.01 (d, 3J
(H,H)~8 Hz, 2 H; H-6, H-12), 7.81 (s, 2 H; H-2, H-8), 7.70 (d,
3J (H,H)~8 Hz, 2 H; H-5, H-11), 4.93–4.78 (m, 2 H; 2 CH-N),
2.56–2.39 (m, 8 H; 2 CH2M,4 CHcyclohex), 1.98–1.20 (m, 60 H; 22
3
CH2, 16 CHcyclohex), 0.81 (t, J (H,H)~7 Hz, 6 H; 2 CH3); 13C
NMR (75 MHz, C2D2Cl4): d~163.25, 163.05, 137.60, 133.32,
132.82, 129.67, 126.71, 126.25, 122.80, 121.86, 120.35, 101.81,
82.00, 53.84, 31.71, 29.52, 29.48, 29.43, 29.16, 29.06, 29.04, 28.92,
28.09, 26.41, 22.51, 20.06, 14.02; UV/Vis (CHCl3): lmax (e)~552
(47320), 511 (27990), 476 (15030), 297 nm (41870 l mol21 cm21);
fluorescence emission (CHCl3, exc.: 552 nm): lem~571 nm; MS
(8 kV, FD): m/z~966.3 (100%) [Mz] (calcd. 966.63).
N,N’-Dicyclohexyl-1,7-bis(2-phenylethynyl)perylene-3,4:9,10-
tetracarboxydiimide (14i). N,N’-Dicyclohexyl-1,7-dibromoper-
ylene-3,4:9,10-tetracarboxydiimide (13a) (500 mg, 0.7 mmol)
and phenylethyne (300 mg, 2.94 mmol) were reacted as described
for (14) to yield the red product (14i) (460 mg, 87%). Mp 165 uC;
1H NMR (500 MHz, CHCl3): d~10.08 (d, 3J (H,H)~8 Hz, 2 H;
H-6, H-12), 8.84 (s, 2 H; H-2, H-8), 8.69 (d, 3J (H,H)~8 Hz, 2 H;
H-5, H-11), 7.64 (m, 4 H; 4 H-Ph), 7.46 (m, 6 H; 6 H-Ph), 5.04
(m, 2 H; 2 N-CH), 2.56 (m, 4 H; 4 CHcyclohex), 1.91 (m, 4 H; 4
CHcyclohex), 1.76 (m, 6 H; 6 CHcyclohex), 1.45 (m, 4 H; 4 CHcyclohex),
1.35 (m, 2 H; 2 CHcyclohex); UV/Vis (CHCl3): lmax (e)~573
(38630), 531 (24850), 494 nm (10750 l mol21 cm21); fluorescence
emission (CHCl3, exc.: 572 nm): lem~590 nm; MS (8 kV, FD):
m/z~754.5 (100%) [Mz] (calcd. 754.28).
N,N’-Di(n-octyl)-1,7-di(dodec-1-ynyl)perylene-3,4:9,10-tetra-
carboxydiimide (14f). N,N’-Di(n-octyl)-1,7-dibromoperylene-
3,4:9,10-tetracarboxydiimide (13b) (2.5 g, 3.2 mmol) and
dodec-1-yne (2.12 g, 12.8 mmol) were reacted as described
for (14) to yield the red product (14f) (2.74 g, 91%). Mp 168 uC;
3
1H NMR (500 MHz, CD2Cl2): d~9.56 (d, J (H,H)~8 Hz, 2
H; H-6, H-12), 8.21 (s, 2 H; H-2, H-8), 8.07 (d, 3J (H,H)~8 Hz,
2 H; H-5, H-11), 4.09 (m, 8 H; 2 CH2-N, 2 CH2M), 1.1 (m, 56 H;
28 CH2), 0.91 (m, 12 H; 4 CH3); 13C NMR (125 MHz, CD2Cl2):
d~162.92, 162.71, 137.74, 133.74, 132.72, 129.62,128.97,
128.32, 128.15, 126.88, 126.81, 126.68, 126.29, 122.72, 122.25,
121.73, 121.37, 120.47, 120.26, 103.12, 82.63, 41.10, 40.86,
32.39, 32.32, 30.26, 30.21, 30.17, 30.12, 30.09, 29.91, 29.81,
29.73, 28.79, 27.66, 23.17, 23.12, 20.73, 14.33, 14.29; UV/Vis
(CHCl3): lmax (e)~552 (47030), 511 (29640), 476 (15680),
297 nm (42420 l mol21 cm21); fluorescence emission (CHCl3,
exc.: 552 nm): lem~571 nm; MS (8 kV, FD): m/z~942.4
(100%) [Mz] (calcd. 942.63); IR (KBr): (cm21)~3028, 3022,
Synthesis of N,N’-dialkyl-5,11-dialkylcoronene-2,3:8,9-
tetracarboxydiimides (9) (Scheme 3)
N,N’-Dialkyl-1,7-dialkynylperylene-3,4:9,10-tetracarboxydiimide
(14) (1 mmol) were dissolved in m-xylene (or toluene) (400 ml).
The solution was deoxygenated by bubbling with argon. DBU
1796
J. Mater. Chem., 2001, 11, 1789–1799

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N,N’-Dicyclohexyl-5,11-di(tridecyl)coronene-2,3:8,9-tetracar-
(0.6 ml) was added through a septum with a syringe. The
reaction mixture was stirred at 100–110 uC for 20 h. After
cooling to room temperature, the solution was poured into ice
cold dilute HCl and the product was extracted with
dichloromethane. The organic layer was washed with water
until neutral, dried over MgSO4 and the solvent evaporated in
vacuo. The crude product was purified by column chromato-
graphy (silica gel–CH2Cl2).
boxydiimide (9d). N,N’-Dicyclohexyl-1,7-di(tridec-1-ynyl)pery-
lene-3,4:9,10-tetracarboxydiimide (14e) (1 g, 1.04 mmol) was
reacted as described for (9) to yield the yellow product (9d)
(945 mg, 95%). DSC: Tm~266 uC, Tiw300 uC; 1H NMR
(500 MHz, CDCl3): d~9.29 (s, 2 H; H-1, H-7), 9.04 (s, 2 H;
H-4, H-10), 8.10 (s, 2 H; H-6, H-12), 5.34 (m, 2 H; 2 CH-N), 3.42
(t, 3J (H,H)~8 Hz, 4 H; 2 Ar-CH2), 2.87 (m, 4 H; 4 CHcyclohex),
2.15 (m, 8 H; 4 CHcyclohex, 2 CH2), 1.93 (m, 6 H; 6 CHcyclohex),
1.75–1.25 (m, 46 H; 6 CHcyclohex, 20 CH2), 0.85 (t, 3J
(H,H)~7 Hz, 6 H; 2 CH3); 13C NMR (125 MHz, CDCl3):
d~164.71 (CLO), 164.47 (CLO), 140.49, 128.73 (CH), 128.73,
128.12, 127.49 (CH), 124.90 (CH), 121.39, 121.12, 120.97, 120.86,
120.16, 118.75, 109.71, 54.55 (CH-N), 33.60, 31.93, 31.15, 30.02,
29.77, 29.68, 29.66, 29.52, 29.38, 26.87, 25.72, 22.69, 14.10
(CH3); UV/Vis (CHCl3): lmax (e)~511 (19231), 477 (9250),
428 (61780), 404 (29760), 382 (7790), 338 (73350), 334 nm
(72760 l mol21 cm21); fluorescence emission (CHCl3, exc.:
477 nm): lem~517 nm; MS (8 kV, FD): m/z~966.7 (100%)
[Mz] (calcd. 966.63); C66H82N2O4 (967.38): calcd. C 81.94, H
8.54, N 2.90, O 6.62%; found C 81.90, H 8.53, N 2.89%.
N,N’-Dicyclohexyl-5,11-didecylcoronene-2,3:8,9-tetracarboxy-
diimide (9a). N,N’-Dicyclohexyl-1,7-di(dodec-1-ynyl)perylene-
3,4:9,10-tetracarboxydiimide (14a) (1 g, 1.13 mmol) was
reacted as described for (9) to yield the yellow product (9a)
(950 mg, 95%). DSC: Tm~245 uC; Ti~w300 uC; 1H NMR
(500 MHz, CDCl3): d~9.24 (s, 2 H; H-1, H-7), 8.99 (s, 2 H;
H-4, H-10), 8.06 (s, 2 H; H-6, H-12), 5.33 (m, 2 H; 2 CH-N),
3.40 (t, 3J (H,H)~7 Hz, 4 H; 2 Ar-CH2), 2.87 (m, 4 H; 4
CHcyclohex), 2.15 (m, 4 H; 4 CHcyclohex), 1.90 (m, 6 H; 6
CHcyclohex), 1.71–1.29 (m, 34 H; 6 CHcyclohex, 14 CH2), 0.88
(t, 3J (H,H)~7 Hz, 6 H; 2 CH3); 13C NMR (75 MHz, C2D2Cl4,
50 uC): d~164.35, 164.13, 140.17, 128.42, 127.76, 127.17,
126.37, 124.62, 121.01, 120.83, 120.65, 120.54, 119.76, 118.38,
54.40, 33.17, 31.71, 30.62, 29.72, 29.54, 29.48, 29.42, 29.15,
26.68, 25.52, 22.48, 13.95; UV/Vis (CHCl3): lmax (e)~511
(19744), 477 (9435), 428 (62092), 404 (30463), 382 (7933), 338
(73176), 334 nm (72780 l mol21 cm21); fluorescence emission
N,N’-Di(n-octyl)-5,11-didecylcoronene-2,3:8,9-tetracarboxy-
diimide (9e). N,N’-Di(n-octyl)-1,7-di(dodec-1-ynyl)perylene-
3,4:9,10-tetracarboxydiimide (14f) (1 g, 1.06 mmol) was reacted
as described for (9) to yield the yellow product (9e) (895 mg,
90%). DSC: Tm~191 uC, Tiw300 uC; 1H NMR (500 MHz,
CDCl3): d~9.28 (s, 2 H; H-1, H-7), 9.06 (s, 2 H; H-4, H-10),
8.22 (s, 2 H; H-6, H-12), 4.41 (t, 3J (H,H)~8 Hz, 4 H; 2
(CHCl3, exc.: 477 nm):
lem~517 nm; MS (8 kV, FD):
m/z~882.4 (100%) [Mz] (calcd. 883.22); C60H70N2O4
(883.22): calcd. C 81.59, H 7.99, N 3.17, O 7.25%; found C
80.85, H 8.01, N 3.09%.
3
N-CH2), 3.48 (t, J (H,H)~8 Hz, 4 H; 2 Ar-CH2), 2.03–1.91
(m, 8 H; 4 CH2), 1.66–1.57 (m, 8 H; 4 CH2), 1.51–1.23 (m, 40 H;
20 CH2), 0.92–0.84 (m, 12 H; 4 CH3); 13C NMR (125 MHz,
C2D2Cl4, 70 uC): d~163.54, 163.31, 140.28, 128.39, 127.86,
127.22, 126.46, 124.50, 121.15, 120.56, 120.21, 119.92, 118.54,
40.87, 33.11, 31.66, 31.63, 30.50, 29.73, 29.49, 29.43, 29.21,
29.08, 28.18, 27.21, 22.41, 13.82; UV/Vis (CHCl3): lmax
(e)~512 (20120), 478 (9640), 428 (60240), 404 (29820), 382
(7950), 338 (70560), 332 (71050 l mol21 cm21); fluorescence
emission (CHCl3, exc.: 477 nm): lem~518 nm; MS (8 kV, FD):
m/z~942.5 (100%) [Mz] (calcd. 942.63); C64H82N2O4 (943.36):
calcd. C 81.49, H 8.76, N 2.97, O 6.78%; found C 81.39, H 8.68,
N 2.94%.
N,N’-Dicyclohexyl-5,11-bis(1-methylbutyl)coronene-2,3:8,9-
tetracarboxydiimide (9b). N,N’-Dicyclohexyl-1,7-bis(3-methyl-
hex-1-ynyl)perylene-3,4:9,10-tetracarboxydiimide
(500 mg, 0.67 mmol) was reacted as described for (9) to yield
(14b)
1
(9b) (445 mg, 89%) as an orange substance. Mpw300 uC; H
NMR (500 MHz, CHCl3): d~10.01 (s, 1 H; Harom.), 9.97 (s, 1
H; Harom.), 9.71 (s, 1 H; Harom.), 9.67 (s, 1 H; Harom.), 8.85 (s, 1
H; Harom.), 8.82 (s, 1 H; Harom.), 5.26 (m, 2 H; CH-N), 4.38 (m,
2 H; 2 CH-Ar), 2.82 (m, 4 H; 4 CHcyclohex), 2.25–1.40 (m, 30 H;
3
16 CHcyclohex, 4 CH2, 2 CH3), 1.06 (t, J (H,H)~7 Hz, 3 H;
CH3), 1.00 (t, 3J (H,H)~7 Hz, 3 H; CH3); 13C NMR (75 MHz,
C2D2Cl4): d~165.12, 164.82, 146.43, 146.32, 129.93, 129.34,
129.27, 128.36, 128.32, 125.51, 125.16, 123.25, 123.16, 121.95,
121.90, 121.65, 121.62, 121.45, 121.42, 121.17, 120.61, 120.53,
54.32, 40.58, 40.35, 34.52, 34.44, 29.25, 26.60, 25.45, 22.30,
22.04, 20.86, 20.80, 20.73, 14.27, 14.21; UV/Vis (CHCl3): lmax
(e)~511 (18470), 477 (8990), 428 (61570), 404 (29080), 382
(7590), 338 (73870), 334 nm (72460 l mol21 cm21); fluorescence
emission (CHCl3, exc.: 477 nm): lem~517 nm; MS (8 kV, FD):
m/z~742.4 (100%) [Mz] (calcd. 742.38).
N,N’-Di(n-octyl)-5,11-di(tridecyl)coronene-2,3:8,9-tetra-
carboxydiimide (9f). N,N’-Di(n-octyl)-1,7-di(pentadec-1-ynyl)pery-
lene-3,4:9,10-tetracarboxydiimide (14g) (1.5 g, 1.4 mmol) was
reacted as described for (9) to yield the yellow product (9f)
(895 mg, 90%). DSC: Tm~177 uC, Tiw300 uC; 1H NMR
(500 MHz, CDCl3): d~9.50 (s, 2 H; H-1, H-7), 9.26 (s, 2 H;
H-4, H-10), 8.40 (s, 2 H; H-6, H-12), 4.46 (t, 3J (H,H)~8 Hz, 4 H;
3
2 CH2-N), 3.60 (t, J (H,H)~8 Hz, 4 H; 2 Ar-CH2), 2.10–1.90
(m, 8 H; 4 CH2), 1.65–1.25 (m, 60 H; 30 CH2), 0.91–0.84 (m, 12 H;
4 CH3); 13C NMR (125 MHz, CDCl3): d~163.83, 163.52, 140.35,
128.54, 127.95, 127.34, 126.63, 124.70, 121.32, 120.73, 120.43,
120.08, 118.74, 40.89, 33.60, 33.12, 31.68, 31.65, 31.16, 30.51,
29.71, 29.45, 29.23, 29.09, 28.19, 27.25, 22.42, 13.81; UV/Vis
(CHCl3): lmax (e)~511 (20210), 477 (9660), 428 (60670), 404
(30040), 382 (7990), 338 (70830), 332 nm (71980 l mol21 cm21);
fluorescence emission (CHCl3, exc.: 477 nm): lem~511 nm; MS
(8 kV, FD): m/z~1026.7 (100%) [Mz] (calcd. 1026.72);
C70H94N2O4 (1027.52): calcd. C 81.82, H 9.22, N 2.73, O 6.23%;
found C 81.76, H 9.25, N 2.64%.
N,N’-Dicyclohexyl-5,11-dihexylcoronene-2,3:8,9-tetracarboxy-
diimide
(9c). N,N’-Dicyclohexyl-1,7-di(oct-1-ynyl)perylene-
3,4:9,10-tetracarboxydiimide (14d) (500 mg, 0.65 mmol) was
reacted as described for (9) to yield the orange product 9c
(480 mg, 96%). Mp w300 uC; 1H NMR (500 MHz, CDCl3):
d~9.44 (s, 2 H; H-1, H-7), 9.18 (s, 2 H; H-4, H-10), 8.26 (s, 2 H;
3
H-6, H-12), 5.35 (m, 2 H; 2 CH-N), 3.52 (t, J (H,H)~8 Hz,
4 H; 2 Ar-CH2), 2.86 (m, 4 H; 4 CHcyclohex), 2.12 (m, 8 H;
4 CHcyclohex, 2 CH2), 2.02–1.88 (m, 6 H; 6 CHcyclohex), 1.72–1.38
(m, 18 H; 6 CHcyclohex, 6 CH2), 0.96 (t, 3J (H,H)~7 Hz, 6 H; 2
CH3); 13C NMR (500 MHz, CDCl3): d~164.85, 164.61,
140.71, 128.97, 128.43, 127.78, 125.16, 124.67, 121.84, 121.35,
121.26, 121.08, 120.59, 51.51, 33.69, 31.77, 31.36, 31.22, 29.64,
29.53, 26.86, 25.71, 22.74, 14.10; UV/Vis (CHCl3): lmax
(e)~511 (18660), 477 (9070), 428 (61690), 404 (29270), 382
(7680), 338 (73480), 334 nm (72769 l mol21 cm21); fluorescence
emission (CHCl3, exc.: 477 nm): lem~517 nm; MS (8 kV, FD):
m/z~770.3 (100%) [Mz] (calcd. 770.41).
N,N’-Bis(2,6-diisopropylphenyl)-5,11-didecylcoronene-2,3:8,9-
tetracarboxydiimide (9g). N,N’-Bis(2,6-diisopropylphenyl)-1,7-
di(dodec-1-ynyl)perylene-3,4:9,10-tetracarboxydiimide (14h)
(1.5 g, 1.45 mmol) was reacted as described for (9) to yield
1
the yellow product (9g) (1.35 g, 90%). Mp 227 uC; H NMR
(500 MHz, C2D2Cl4, 100 uC): d~10.21 (s, 2 H; H-1, H-7), 9.96
(s, 2 H; H-4, H-10), 9.05 (s, 2 H; H-6, H-12), 7.48 (t, 3J
J. Mater. Chem., 2001, 11, 1789–1799
1797

View Online
H; 3 CH3); 13C NMR (125 MHz, CDCl3): d~163.45, 145.73,
3
(H,H)~8 Hz, 2 H; 2 Ar-H), 7.35 (d, J (H,H)~8 Hz, 4 H; 4
Ar-H), 3.88 (t, 3J (H,H)~8 Hz, 4 H; 2 Ar-CH2), 2.95 (septet, 3J
(H,H)~7 Hz, 4 H; 4 CHisopropyl), 2.19 (m, 4 H; 2 CH2), 1.66 (m,
4 H; 2 CH2), 1.46 (m, 4 H; 2 CH2), 1.36–1.20 (m, 32 H; 10 CH2,
4 (CH3)isopropyl), 0.78 (t, 3J (H,H)~7 Hz, 6 H; 2 CH3); 13C
NMR (125 MHz, C2D2Cl4, 100 uC): d~165.40, 165.14, 146.49,
142.71, 131.95, 131.15, 130.63, 130.07, 129.85, 129.13, 127.41,
124.99, 124.48, 123.80, 123.64, 122.62, 122.42, 122.35, 34.41,
34.35, 32.19, 32.03, 30.27, 29.95, 29.93, 29.85, 29.59, 29.48,
24.48, 24.46, 24.33, 24.20, 22.92, 4.30; UV/Vis (CHCl3): lmax
(e)~511 (19890), 477 (8920), 429 (69050), 404 (30810), 382
(6960), 338 (71810), 333 nm (76770 l mol21 cm21); fluorescence
emission (CHCl3, exc.: 477 nm): lem~518 nm; MS (8 kV, FD):
m/z~1039.0 (100%) [Mz] (calcd. 1038.63); C72H82N2O4
(1039.45): calcd. C 83.20, H 7.95, N 2.70, O 6.16%; found C
82.72, H 8.26, N 2.73%.
138.47, 138.45, 137.15, 136.85, 133.27, 130.82, 129.83, 129.53,
129.50, 128.85, 128.75, 128.57, 128.08, 127.37, 127.16, 126.16,
125.08, 124.01, 119.76, 118.92, 99.21, 97.86, 97.64, 82.62, 82.56,
78.92, 31.89, 29.60, 29.58, 29.54, 29.32, 29.30, 29.22, 29.17, 29.09,
28.84, 28.38, 23.96, 22.66, 20.10, 19.97, 14.07; UV/Vis (CHCl3):
lmax (e)~549 (61230), 519 (49160), 343 (34300), 285 nm
(47200 l mol21 cm21); fluorescence emission (CHCl3, exc.:
520 nm): lem~589 nm; MS (8 kV, FD): m/z~973.7 (100%)
[Mz] (calcd. 973.67); C70H87NO2 (974.46): calcd. C 86.28, H
9.00, N 1.44, O 3.28%; found C 86.27, H 8.97, N 1.37%.
N-(2,6-Diisopropylphenyl)-6,11-didecyl-8-dodecynyl-2,3-coron-
(19)
enedicarboximide
(20). Trialkynylperylene
(1.9 g,
1.95 mmol) was dissolved in toluene (600 ml) and the solution
was deaerated by bubbling with argon. DBU (3.1 ml) were
added with a syringe through a septum. After stirring for 24 h
at 110 uC the solution was poured into the same amount of
diluted HCl (HCl : H2O~1 : 3) and the product was extracted
with dichloromethane. The organic layer was dried over
MgSO4 and the solvent was evaporated. The crude product
was purified by column chromatography on silica gel (CH2Cl2–
petroleum ether~1 : 1) and the yellow product was isolated
(1.25 g, 65%). DSC: Ti~269 uC; 1H NMR (500 MHz, C2D2Cl4,
100 uC): d~9.83 (s, 1 H; Harom.), 9.80 (s, 1 H; Harom), 9.39 (d, 3J
Synthesis of coronenemonoimides (10)
Tribromoperylenemonoimide (18). N-(2,6-Diisopropylphenyl)-
perylene-3,4-dicarboximide (17) (10 g, 21 mmol) was dissolved in
chloroform (1.5 l), bromine (60 ml) was added dropwise and the
mixture was stirred for 6 h at reflux temperatures. After cooling to
room temperature the solution was added to a vigorously stirred
mixture of water (3 l), KOH (25 g) and Na2SO2 (15 g). KOH and
Na2SO2 were added carefully in portions until the color changed
from brown to bright orange. The organic layer was separated
and the aqueous layer was extracted with chloroform. The
combined organic solutions were dried over MgSO4 and the
solvent was evaporated leaving the crude product (13 g, 86%),
which was then purified in portions of 4 g each by column
chromatography (silica gel, petroleum ether : CH2Cl2~1:1). Mp
w300 uC; 1H NMR (250 MHz, CD2Cl2): d~9.42 (d, 3J
3
(H,H)~9 Hz, 1 H; Harom.), 9.09 (s, 1 H; Harom.), 9.07 (d, J
(H,H)~9 Hz, 1 H; Harom), 8.86 (s, 1 H; Harom.), 8.81 (s, 1 H;
Harom.), 7.51 (t, 3J (H,H)~8 Hz, 1 H; H-b), 7.38 (d, 3J
3
(H,H)~8 Hz, 2 H; 2 H-a), 3.75 (t, J (H,H)~8 Hz, 2 H; Ar-
CH2), 3.70 (t, 3J (H,H)~7.7 Hz, 2 H; Ar-CH2), 3.01 (septet, 3J
(H,H)~6.5 Hz, 2 H; 2 CHisopropyl), 2.84 (t, 3J (H,H)~7.5 Hz, 2
H; CH2M), 2.18–2.12 (m, 4 H; 2 CH2), 1.96–1.93 (m, 2 H; CH2),
1.78–1.60 (m, 6 H; 3 CH2), 1.55–1.26 (m, 36 H; 18 CH2), 1.24
(d, 3J (H,H)~7 Hz, 12 H; 4 (CH3)isopropyl), 0.89–0.83 (m, 9 H; 3
CH3); 13C NMR (125 MHz, C2D2Cl4, 100 uC): d~165.62,
165.59, 146.51, 139.98, 139.42, 132.38, 130.54, 130.26, 129.86,
129.52, 128.73, 128.22, 128.16, 127.98, 127.92, 126.97, 126.86,
124.32, 123.63, 123.42, 123.38, 123.36, 123.26, 122.87, 122.60,
122.05, 121.20, 120.80, 120.72, 98.56, 80.19, 34.41, 34.13, 32.21,
32.15, 31.64, 31.42, 30.26, 30.18, 29.97, 29.95, 29.92, 29.90,
29.75, 29.64, 29.61, 29.55, 29.54, 29.47, 24.39, 22.92, 22.88,
20.51, 14.27, 14.25; UV/Vis (CHCl3): lmax (e)~480 (12070),
450 (11850), 426 (40180), 403 (23250), 345(60010), 335 nm
3
(H,H)~8 Hz, 1 H; Ar-H), 9.21 (d, J (H,H)~8 Hz, 1 H; Ar-
H), 8.92 (s, 1 H; Ar-H), 8.91 (s, 1 H; Ar-H), 8.51 (d, 3J
(H,H)~8 Hz, 1 H; Ar-H), 8.04 (d, 3J (H,H)~8 Hz, 1 H; Ar-H),
7.89 (m, 1 H; Ar-H), 7.53 (t, 3J (H,H)~7 Hz, 1 H; Ph-H), 7.36 (d,
3J (H,H)~7 Hz, 2 H; 2 Ph-H), 2.75 (m, 2 H; 2 CHisopropyl), 1.21 (d,
3J (H,H)~7 Hz, 6 H; 2 (CH3)isopropyl); 13C NMR (75 MHz,
CD2Cl2): d~162.75, 146.14, 138.37, 135.49, 135.27, 131.61,
130.97, 130.88, 130.74, 130.28, 129.94, 129.76, 129.73, 129.05,
127.63, 127.07, 126.85, 126.39, 124.24, 121.07, 121.02, 119.28,
119.07, 29.29, 23.78; MS (8 kV, FD): m/z~716.0 (100%) [Mz]
(calcd. 714.94); C34H24NO2Br3 (718.28): calcd. C 56.85, H 3.37, N
1.95, Br 33.37, O 4.45%; found C 56.56, H 3.50, N 1.92, Br
32.75%.
(81150 l mol21 cm21);
exc~426 nm): lem~486 nm; MS (8 kV, FD): m/z~974.0
(100%) [Mz] (calcd. 973.67).
fluorescence
emission
(CHCl3,
l
N-(2,6-Diisopropylphenyl)-1,6,9-tri(dodec-1-ynyl)perylene-3,4-
dicarboximide (19). N-(2,6-Diisopropylphenyl)-1,6,9-tribromo-
perylenedicarboximide (18) (1 g, 1.4 mmol) was dissolved
in a mixture of dry THF (250 ml) and dry triethylamine
(250 ml) in an argon atmosphere. Pd(PPh3)4 (194 mg,
1.68 mmol, 12 mol%) and CuI (40 mg, 2.1 mmol, 15 mol%)
were added under argon atmosphere. Finally dodec-1-yne
(903 mg, 5.4 mmol) was addedd via syringe through a septum.
After stirring at 60 uC for 12 h the mixture was poured into the
same amount of cold dilute HCl (HCl: H2O~1 : 3) and the
product was extracted with dichloromethane. The organic layer
was extracted with water until the aqueous layer was neutral.
The crude product was purified by column chromatography on
silica gel (CH2Cl2–petroleum ether~1 : 1) to yield pure (19)
(1.1 g, 80%) as red powder. 1H NMR (500 MHz, CDCl3):
N-(2,6-Diisopropylphenyl)-6,11-didecyl-8-dodecylcoronene-2,3-
dicarboximide (10). Coronenemonoalkyne (20) (390 mg,
0.4 mmol) was dissolved in THF (200 ml) and the solution
was deaerated by alternately evacuating and flushing with
argon several times. Palladium on charcoal (200 mg) was added
under argon atmosphere, and the flask was evacuated and then
flushed with hydrogen gas. The reaction mixture was stirred at
room temperature and the course of the hydrogenation was
monitored by FD mass spectrometry. After 1 h the reaction
was complete and the solution was filtered through Celite and
the solvent was evaporated. The crude product was dissolved in
CHCl2 and on addition of methanol the yellow product
(350 mg, 90%) precipitated. DSC: Ti~160 uC; 1H NMR
(500 MHz, C2D2Cl4, 100 uC): d~9.82 (s, 1 H; Harom.), 9.80
3
(s, 1 H; Harom.), 9.15 (d, J (H,H)~9 Hz, 1 H; H-9 or H-10),
d~9.90 (d, 3J (H,H)~8 Hz,
1
H; H-12), 9.78 (d, 3J
9.08 (d, 3J (H,H)~9 Hz, 1 H; H-9 or H-10), 8.88 (s, 1 H;
3
(H,H)~8 Hz, 1 H; H-7), 8.72 (s, 1 H; H-2 or H-5), 8.71 (s, 1
H; H-2 or H-5), 8.45 (d, 3J (H,H)~8 Hz, 1 H; H-10), 7.69 (m, 2
H; H-8, H-11), 7.45 (t, 3J (H,H)~8 Hz, 1 H; Ph-H), 7.30 (d, 3J
(H,H)~8 Hz, 2 H; 2 Ph-H), 2.70 (septet, 3J (H,H)~7 Hz, 2 H; 2
CHisopropyl), 2.62–2.53 (m, 6 H; 3 CH2M), 1.75–1.67 (m, 6 H; 3
CH2), 1.56–1.47 (m, 6 H; 3 CH2), 1.38–1.23 (m, 36 H; 18 CH2),
1.14 (d, 3J (H,H)~7 Hz, 12 H; 4 (CH3)isopropyl), 0.87–0.82 (m, 9
H
arom.), 8.84 (s, 1 H; Harom.), 8.82 (s, 1 H; Harom.), 7.47 (t, J
(H,H)~8 Hz, 1 H; Ph-H), 7.34 (d, 3J (H,H)~8 Hz, 2 H; 2 Ph-
H), 3.78–3.69 (m, 6 H; 3 Ar-CH2), 2.96 (septet, 3J (H,H)~
7 Hz, 2 H; 2 CHisopropyl), 2.17-2.08 (m, 6 H; 3 CH2), 1.65–1.62
(m, 6 H; 3 CH2), 1.50–1.45 (m, 6 H; 3 CH2), 1.39–1.19 (m, 46 H;
17 CH2, 4 (CH3)isopropyl), 0.82 (t, 3J (H,H)~7 Hz, 9 H; 3 CH3);
13C NMR (125 MHz, C2D2Cl4, 100 uC): d~166.72, 147.52,
1798
J. Mater. Chem., 2001, 11, 1789–1799

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D. Pressner, C. Go¨ltner, H.-W. Spiess and K. Mu¨llen, Ber.
Bunsenges. Phys. Chem., 1993, 97, 1362; C. Go¨ltner, D. Pressner,
K. Mu¨llen and H.-W. Spiess, Angew. Chem., 1993, 105(11), 1722;
C. Go¨ltner, D. Pressner, K. Mu¨llen and H.-W. Spiess, Angew.
Chem., Int. Ed. Engl., 1993, 32(11), 1660; P. Schlichting, U. Rohr
and K. Mu¨llen, J. Mater. Chem., 1998, 8, 2651.
9
141.34, 140.77, 140.54, 133.45, 131.41, 131.29, 131.16, 130.47,
129.14, 128.81, 128.75, 125.58, 125.28, 125.10, 124.88, 124.71,
124.30, 124.22, 124.05, 124.01, 122.72, 122.23, 121.63, 121.29,
35.87, 35.36, 33.14, 32.89, 32.60, 31.26, 31.22, 30.91, 30.71,
30.53, 25.37, 23.86, 15.23; UV/Vis (CHCl3): lmax (e)~475
(10480), 446 (8860), 418 (33020), 399 (18760), 343 (82030),
334 nm (73010 l mol21 cm21); fluorescence emission (CHCl3,
10 R. A. Cormier and B. A. Gregg, Chem. Mater., 1998, 10, 1309.
11 H. Bengs, F. Closs, T. Frey, D. Funhoff, H. Ringsdorf and
K. Siemensmeyer, Liq. Cryst., 1993, 15(5), 565; D. Adam,
P. Schuhmacher, J. Simmerer, L. Ha¨ussling, K. Siemensmeyer,
K. H. Etzbach, H. Ringsdorf and D. Haarer, Nature, 1994, 371,
141; D. Adam, F. Closs, T. Frey, D. Funhoff, D. Haarer,
H. Ringsdorf, P. Schuhmacher and D. Siemensmeyer, Phys. Rev.
Lett., 1993, 70(4), 457; F. Closs, K. Siemensmeyer, T. Frey and
D. Funhoff, Liq. Cryst., 1993, 14(3), 629.
lexc~415 nm): lem~482 nm; MS (8 kV, FD): m/z~977.9
(100%) [Mz] (calcd. 977.70); IR (KBr): (cm21)~3067,
3033, 2958, 2923, 2852, 1706, 1666, 1629, 1595, 1468, 1443,
1337, 1260, 1191, 1097, 1057, 1019, 923, 865, 800, 766, 721;
C70H91NO2 (978.49): calcd. C 85.92, H 9.37, N 1.43, O 3.27%;
found C 85.35, H 9.41, N 1.39%.
12 U. Rohr, P. Schlichting, A. Bo¨hm, M. Groß, K. Meerholz,
C. Bra¨uchle and K. Mu¨llen, Angew. Chem., 1998, 110(10), 1463;
U. Rohr, P. Schlichting, A. Bo¨hm, M. Groß, K. Meerholz,
C. Bra¨uchle and K. Mu¨llen, Angew. Chem., Int. Ed., 1998, 37(10),
1434.
Acknowledgements
Financial support of this work by the BASF AG, the Fonds der
Chemie and the Volkswagenstiftung is gratefully acknowl-
edged.
13 P. Schlichting, U. Rohr and K. Mu¨llen, Liebigs Ann./Recl., 1997,
395.
14 In all schemes only the major isomer of 9, 12, 13 and 14 is shown.
15 Semiempirical calculations made by Dr P. Erk (BASF AG) could
relate the absorption bands with the electonic transitions:
P. Schlichting, PhD thesis, University of Mainz, 1998.
16 Synthesis of perylenemonoimides: Y. Nagao and T. Misono, Bull.
Chem. Soc. Jpn., 1981, 54, 1191; Y. Nagao and T. Misono, Bull.
Chem. Soc. Jpn., 1981, 54, 1575.
17 P. G. Schouten, J. M. Warman, M. P. de Haas, M. A. Fox and
H. Pan, Nature, 1991, 353, 736; P. G. Schouten, J. M. Warman,
M. P. de Haas, C. F. van Nostrum, G. H. Gelinck, R. J. M. Nolte,
M. J. Kopijn, J. W. Zwikker, M. K. Engel, M. Hanack,
Y. H. Chang and W. T. Ford, J. Am. Chem. Soc., 1994, 116,
6880; A. M. van de Craats, P. G. Schouten and J. M. Warman,
EKISHO, J. Jap. Liq. Cryst. Soc., 1998, 2, 12; A. M. van de
Craats, J. M. Warman, M. P. de Haas, J. Simmerer, D. Haarer and
P. Schumacher, Adv. Mater., 1996, 8, 823.
18 A. M. van de Craats, J. M. Warman, A. Fechtenko¨tter, J. D. Brand,
M. A. Harbison and K. Mu¨llen, Adv. Mater., 1999, 17, 1469.
19 A. M. van de Craats, J. M. Warman, P. Schlichting, U. Rohr,
Y. Geerts and K. Mu¨llen, Synth. Met., 1999, 102, 1550.
20 G. Horowitz, F. Kouki, P. Spearman, D. Fichou, C. Nogues and
X. Pan, Adv. Mater., 1996, 8, 242; P. Ranke, I. Bleyl, J. Simmerer,
D. Haarer, A. Bacher and H. W. Schmidt, Appl. Phys. Lett., 1997,
71, 1332.
References
1
F. Graser and E. Ha¨dicke, Liebigs Ann. Chem., 1980, 1994;
F. Graser and E. Ha¨dicke, Liebigs Ann. Chem., 1980, 483;
Y. Nagao and T. Misono, Dyes Pigm., 1984, 5, 171;
A. Rademacher, S. Ma¨rkle and H. Langhals, Chem. Ber., 1982,
115, 2927; H. Zollinger, Color Chemistry, 2nd ed., VCH,
Weinheim, 1991; R. M. Christie, Polym. Int., 1994, 34, 351.
H. O. Loufty, A. M. Hor, P. Kazmaler and M. J. Tarn, J. Imag.
Sci., 1989, 33, 151.
G. Seybold and G. Wagenblast, Dyes Pigm., 1989, 11, 303;
H. Langhals, Nachr. Chem. Tech. Lab., 1980, 28, 716.
D. Schlettwein, D. Wo¨hrle, E. Kaarmann and U. Melville, Chem.
Mater., 1994, 6, 3.
M. P. O’Neil, M. P. Niemczyk, W. A. Svec, D. Gosztola,
G. L. Gaines and M. R. Wasielewski, Science, 1992, 257, 63.
R. Reisfeld and G. Seybold, Chimia, 1990, 44, 295; M. Sandrai,
L. Hadel, R. R. Sauers, S. Husain, K. Krogh-Jespersen,
J. D. Westbrook and G. R. Bird, J. Phys. Chem., 1992, 96,
7988; R. Gvishi, R. Reisfeld and Z. Burshtein, Z. Chem. Phys.
Lett., 1993, 213, 338.
2
3
4
5
6
7
8
H. Quante and K. Mu¨llen, Angew. Chem., 1995, 107, 1487; H. Quante
and K. Mu¨llen, Angew. Chem., Int. Ed. Engl., 1995, 34, 1323.
F. O. Holtrup, G. R. J. Mu¨ller, H. Quante, S. De Feyter, F. De
Schryver and K. Mu¨llen, Chem. Eur. J., 1997, 3, 219.
21 P. G. Schouten, J. M. Warman and M. P. de Haas, J. Phys. Chem.,
1993, 97, 9863.
J. Mater. Chem., 2001, 11, 1789–1799
1799