Novel core-expanded rylenebis(dicarboximide) dyes bearing pentacene units: Facile synthesis and photophysical properties

Article abstract of DOI:10.1002/chem.200700523

Two synthetic routes for the benzannulation in the "bay"-region of rylenebis(dicarboximide)s leading to new π-system-expanded chromophores are described. The first route follows a two-step approach: Suzuki coupling of bromo-substituted perylenebis(dicarbo

Full text of DOI:10.1002/chem.200700523

FULL PAPER
DOI: 10.1002/chem.200700523
Novel Core-Expanded Rylenebis(Dicarboximide) Dyes Bearing Pentacene
Units: Facile Synthesis and Photophysical Properties
Yuri Avlasevich,[a] Sibylle Müller,[a] Peter Erk,[b] and Klaus Müllen*[a]
Abstract: Two synthetic routes for the
benzannulation in the “bay”-region of
rylenebis(dicarboximide)s leading to
new p-system-expanded chromophores
are described. The first route follows a
two-step approach: Suzuki coupling of
is best described as a palladium-assist-
ed cycloaddition of benzyne, formed in
situ, to the bay-region of the bromo-
substituted rylene core. Two new types
of core-expanded rylene dyes were syn-
thesised: yellow dibenzocoronenebis-
(dicarboximide)s, absorbing at 490 nm,
and a green dinaphthoquaterrylenebis-
(dicarboximide), which absorbs at
700 nm. These new chromophores are
characterised by significant hypsochro-
mic shifts of absorption, compared to
their parent rylenebis(dicarboximide)s,
excellent photostabilities and high fluo-
rescence quantum yields.
AHCTREUNG
AHCTREUNG
bromo-substituted
perylenebis(dicar-
Keywords: absorption · benzannu-
boximide) with 2-bromophenylboronic
acid, followed by palladium-catalysed
dehydrobromination. The second route
lation
· dyes/pigments · fluores-
cence · perylenes · quaterrylene
Introduction
Rylenebis(dicarboximide) chromophores 1 possess excep-
tional chemical, thermal and photochemical stabilities with
high extinction coefficients.[1] Their use has been explored
for demanding applications such as optoelectronic[2] and
photovoltaic[3] devices, thermographic processes,[4] energy-
transfer cascades,[5] light-emitting diodes[6] and NIR-absorb-
ing systems.[7] Extension of the aromatic system along the
long molecular axis from perylene- (PDI), 1a (n=0), to ter-
rylene- (TDI), 1b (n=1)[8] and quaterrylenebis(dicarboxi-
mide)s (QDI), 1c (n=2)[9] induced a bathochromic shift of
about 100 nm per additional naphthalene unit reaching an
absorbance maximum of 780 nm for the quaterrylene 1c
and a nearly linear increase of the extinction coefficient up
to 170000mÀ1 cmÀ1. Very recently, the syntheses of two
higher rylene homologues, which each have an intensive ab-
sorption in the NIR region, were reported: pentarylene-
(1d, n=3, lmax =877 nm) and hexarylenebis(dicarboximide)s
(1e, n=4, lmax =950 nm).[10]
[a] Dr. Yu. Avlasevich, Dr. S. Müller, Prof. Dr. K. Müllen
Max Planck Institute for Polymer Research
Ackermannweg 10, 55128 Mainz (Germany)
Fax : (+49)6131-379350
E-mail: muellen@mpip-mainz.mpg.de
[b] Dr. P. Erk
BASF Aktiengesellschaft
67056 Ludwigshafen (Germany)
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A bathochromic shift of the absorption was also obtained
by expanding the p system of perylenebis(dicarboximide)s
along the short molecular axis. Benzannulation in the
“bay”-region of rylenes with the introduction of anthracene
(2, lmax =701 nm) or tetracene (3, lmax =1018 nm) elements
resulted in significant bathochromic shifts of the absorption
maximum, presumably due to the nonplanarity of the mole-
cules formed.[11–13] The absorption of dibenzoperylenebis(di-
Results and Discussion
Syntheses
Two-step benzannulation of PDIs: The two-step benzannula-
tion of 1,7-dibromoperylenebis(dicarboximide) 8 has been
previously reported:[16] bromination of perylene 3,4:9,10-bis-
anhydride led to 1,7-dibromoperylene bisanhydride 7, which
carboximide)[11]
2
and dibenzopentarylenebis(dicarboxi-
contains various amounts of the corresponding 1,6-isomer
depending on the reaction conditions.[17] In contrast to the
coronenebis(dicarboximide) synthesis,[18] both isomers react-
ed to form the same desired product in the case of benzan-
nulation, which is a major advantage of this synthesis. The
1,7-dibromoperylenebis(dicarboximide)s 8a–c were obtained
by imidisation of the anhydride 7 with aryl or alkyl
amines.[14,18] The reaction of 1,7-dibromoperylenebis(dicar-
boximide)s 8a,b with 2-bromophenylboronic acid under
Suzuki conditions afforded the perylene derivatives 9a,b in
53% yield (Scheme 1). Self-reaction of 2-bromophenylbor-
onic acid is known not to occur under these conditions.[19]
One- and twofold debrominated products of 9 were ob-
served in minor amounts (less than 10%), but this mixture
mide)[13] 3 was shifted by about 180 nm relative to the pery-
lene 1a (lmax =524 nm) and pentarylene 1d (lmax =830 nm)
derivatives, respectively.[10] However, enlargement of the p
system did not always promote a shift to longer wavelengths.
The coronenebis(dicarboximide)s (CDI) 4 can be regarded
as perylenebis(dicarboximide)s expanded along the short
molecular axis. Their absorbances were hypsochromically
shifted by 20–100 nm, relative to that of the perylene 1a, to
a maxima at 511 (low intensity band) and 428 nm (high in-
tensity band), leading to a yellow colour.[14] Stable, yellow
chromophores with high molar extinction coefficients are
generally difficult to obtain as the extinction coefficient
often increases with the size of the aromatic system, which
generally necessitates that these
dyes absorb more bathochromi-
cally.[1c] Basic chemical modifi-
cation of the red perylene core
facilitates a hypsochromic shift
of the absorption to the yellow.
Diverse methodologies to func-
tionalise the perylene aromatic
core are a topic of current re-
search to extend the range of
application of these chromo-
phores as functional dyes or im-
prove their performance in de-
vices.
Perylenebis(dicarboxi-
mide)s, functionalised in one
bay-region, through cycloaddi-
tion reactions followed by re-
duction or mono-nitration and
cyclisation, are known.[15] An
additional core-expansion from
coronenebis(dicarboximide)s
4
to dibenzocoronenebis(dicar-
boximide)s 5 shifted the ab-
sorption to the red.[16] However,
the yellow colour in solution re-
mained and became brighter
due to the absence of residual
absorption above 500 nm.
Scheme 1. Reagents, conditions and yields: i) 1-heptyloctylamine, NMP, 1508C, 4H, 39%; ii) 2-bromophenyl-
boronic acid, [Pd
A
ACHTREUNG
1608C, overnight, 46%; iv) 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, [Pd
1108C, 24 h, 80%.
A
ACHTREUNG
Herein, we report two syn-
thetic routes to enlarge the aromatic p system of available
rylene derivatives, leading to two novel chromophores with
hypsochromically shifted absorption, namely the dibenzocor-
onenebis(dicarboximide) 5, and dinaphthoquaterrylenebis-
was directly used for the next step successfully. The palladi-
um-catalysed dehydrohalogenation[20] with 1,8-diazabicyclo-
A
furnished dibenzocoronenebis(dicarboximide)s 5a,b in 46%
A
yield as yellow solids.
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Dyes/Pigments
FULL PAPER
One-step benzannulation of
PDIs: The appeal of these new
yellow chromophores is slightly
diminished by the moderate
yields during their syntheses.
The Suzuki coupling in the first
step is accompanied by side re-
actions, even under mild condi-
tions, whereas a high yield in
the second step is prevented by
the drastic conditions of the
palladium-induced dehydrobro-
mination. Simplification of the
procedure was achieved by the
core-extension of the bay-
region of PDI by means of a
one-step Diels–Alder cycloaddi-
tion.[21] Recently, an effective
route for the benzannulation of
2-halobiaryls, with in situ gener-
ation of arynes, was de-
scribed.[22] This reaction was
successfully applied for the syn-
thesis of carbo- and heterocy-
clic polyaromatic molecules in
good yields. The bay-region of
Scheme 2. Reagents, conditions and yields: i) Br2, chloroform, 558C, 60 h, 84%; ii) tert-octylphenol, K2CO3,
NMP, 48 h, 85%; iii) 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, [Pd
2 4 h, 46%.
A
E
dibromoPDIs 8 is apparently synthetically equivalent to the
2-halobiaryls. The reaction of the commercially available 2-
(trimethylsilyl)phenyl trifluoromethanesulfonate and N,N’-
should be noted that precursor 11 was more susceptible to
the basic conditions upon heating than 8. As such, a lower
reaction temperature was used (958C instead of 1108C for
the PDI 8) in order to avoid debromination of 11.
dioctyl-1,7-dibromoperylenebis(dicarboximide)
(8c)[18]
under the conditions described above[22] afforded dibenzo-
coronene bis(dicarboximide) 5c in high yield (80%) as a
light-brown solid. The product 5c precipitated almost quan-
titatively from the reaction mixture upon cooling to room
temperature, which opens the possibility for the industrial
application of the benzannulation of 1,7-dibromoPDIs, since
these compounds are readily accessible.[17,18]
Photophysical properties
Dibenzocoronenebis(dicarboximides): Both coronene deriva-
tives 4 and 5 are soluble in common organic solvents such as
dichloromethane, chloroform or toluene. In the region of
shorter wavelengths, up to 400 nm, the spectrum of the di-
benzoCDI 5 shows a sharp band with a defined structure at
349 nm, whereas the band with a maximum absorbance of
338 nm in the spectrum of 4 is broad (Figure 1). Only one
band with the typical perylene vibronic structure is seen at
Core extension of quaterrylenebis(dicarboximides): Quater-
rylene bis(dicarboximides) are known as green NIR dyes
that possess high thermal and photochemical stabilities as
well as high molar absorptivities.[9] However, their fluores-
cence quantum yields and solubilities are quite low. An in-
crease of solubility could be achieved by the bromination of
bay-region and subsequent phenoxylation of the bromides.[8]
Bromination of QDI 1c with an excess of molecular bro-
mine afforded the hexabrominated product 10 (Scheme 2).
The hexabromide 10 possesses an enhanced solubility rela-
tive to 1c, but a lower photochemical stability. It was found
that only bromides closest to the imide positions (1,6,11,16)
were substituted with the phenoxy groups upon phenoxyla-
tion. The two “inner” bromides remained even after the
long reaction times and drastic conditions. The dibromoQDI
11 is synthetically analogous to the PDIs 8; therefore, the
bromides are suitable for the palladium-promoted benzan-
nulation. The core expansion of 11 under the same condi-
tions as for 8 afforded core-modified QDI 6 in 46% yield. It
Figure 1. Absorption spectra of coronenebis(dicarboximide) 4 (dashed
line), dibenzocoronenebis(dicarboximide) 5a (solid line) and PDI 1a
(dotted line).
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K. Müllen et al.
longer wavelength with an absorbance maximum at 494 nm
(e=66000mÀ1 cmÀ1), giving rise to the yellow colour. The
yellow solution of dibenzoCDI 5a appears brighter and
greener than that of the CDI 4, given that there is no ab-
sorbance above 515 nm for 5. The value of e for 5 at 494 nm
is similar to that of 4 at 428 nm (e=62000 mÀ1 cmÀ1).[18] Di-
benzocoronenebis(dicarboximide)s 5a,b have a bright fluo-
rescence with a quantum yield of 80% (see Experimental
Section), high with respect to other yellow fluorophores; for
example, acridine yellow, which has a fluorescence quantum
yield of 47%.[23] The emission spectrum of the dibenzoCDI
5c (Figure 2) shows the mirror symmetry with the absorp-
tion spectrum, and a Stokes shift of 13 nm.
was reported for the parent QDI,[9] the absorption of such
dyes is additionally influenced by the phenoxy substitution
in the bay. The bathochromic shift for tetraphenoxyQDI 1c
is 19 nm with respect to the unsubstituted dye. Therefore,
the lmax for the parent dinaphthoQDI, bearing no phenyl
ether moieties, is expected to be near 680 nm. The peak at
411 nm is caused by the four phenyl ethers that affect the
slight nonplanarity of the polyaromatic macrocycle, similar
to the parent QDI.[9] Dinaphthoquaterrylenebis(dicarbox-
A
726 nm and a quantum yield of 40%.
Electronic properties: The absorption properties of the de-
scribed rylene derivatives can be understood with support of
semiempirical quantum mechanical calculations (Table 1).
Table 1. Calculated HOMO–LUMO energy levels[a] and lmax values[a,b]
for dyes 1a, 1b, 1c, 4, 5 and 6.
HOMO LUMO HOMO–LUMO gap lmax calcd[a,b] lmax exptl
1a À8.85
1b À8.17
1c À7.86
À3.125.75209 4
À3.125.05
À3.25
52
603
4.61
6.26
5.79
4.80
650
693
455
492
622
760
511
4
5
6
À9.01
À8.65
À7.93
À2.75
À2.86
494
À3.13
701[c]
[a] HyperChem 6, PM3. [b] Single excited state, 20 occupied and 20 unoc-
cupied orbitals. [c] Tetraphenoxy substituted.
Figure 2. Absorption (solid line) and emission (dashed line) spectra of di-
benzocoronenebis(dicarboximide) 5c (solvent: chlorobenzene, T=
373 K).
Within the homologous series of rylenebis(dicarboximide)s,
the energy level of the LUMO is barely influenced by the
extension of the aromatic system, whereas the HOMO
energy is increased with each additional naphthalene unit,
leading to a smaller HOMO–LUMO gap and a bathochrom-
ically shifted absorption maximum. This increase in energy
of the HOMOs is attributed to the increasing number of an-
tibonding connections between the naphthalene moieties.[24]
The calculated frontier orbitals of coronenebis(dicarbox-
Dinaphthoquaterrylenebis(dicarboximide): A comparison of
the absorption spectra of the newly synthesised dinaphthoQ-
DI 6 (Figure 3) shows a significant hypsochromic shift of ab-
imide) show already that CDI cannot be regarded as a
simple analogue of rylenebis(dicarboximide)s (Figure 4).
The formal fusion of a perylenebis(dicarboximide) with
two ethylenes in the bay-region leads to a totally different
appearance of the HOMO orbital coefficients of CDI com-
pared to PDI, whereas the LUMO of CDI matches the
LUMO of PDI. Regarding the orbitals of the pure hydrocar-
bon coronene, it becomes evident that the HOMO of CDI
is comparable with the HOMO of coronene. As previously
mentioned, the absorption spectrum of a CDI shows two
main bands in the region above 350 nm, instead of only one
as in the case for PDI. Hence, this absorption behaviour is a
result of a mixture of perylenebis(dicarboximide)- and coro-
nene-like orbitals: the band at 511 nm, corresponding to the
HOMO–LUMO transition according to the calculation, is
therefore caused by a transition from a coronene-like
HOMO to a perylene-like LUMO. The second band at
429 nm shows the typical vibronic fine structure of perylene-
bis(dicarboximide)s, as this band is related to the transition
between the perylene-like NHOMO and the perylene-like
Figure 3. Absorption (solid line) and emission (dashed line) spectra of di-
naphthoquaterrylenebis(dicarboximide) 6 and absorption spectrum of its
precursor 11 (dotted line, solvent: toluene).
sorption maximum as compared to the precursor 11 (from
758 to 700 nm). This phenomenon is accompanied by a
blue-green appearance in solution (chloroform, toluene).
The value of the extinction coefficient is lower than for the
precursor, but still remains high (e=143000mÀ1 cmÀ1). As
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Dyes/Pigments
FULL PAPER
Conclusion
The syntheses of two novel chromophores are detailed,
namely the dibenzocoronenebis(dicarboximide)s 5 and the
dinaphthoquaterrylenebis(dicarboximide) 6, by short and
facile routes. The palladium-catalysed ring annulation reac-
tion enabled the enlargement of the aromatic p system and
has thereby led to new chromophores based on core-extend-
ed rylene dyes. The optical properties of the newly synthes-
ised dyes are in good agreement with the results of semiem-
pirical quantum mechanical calculations. Sharp absorption
bands between 400 and 500 nm led to a brilliant greenish-
yellow appearance with an intensive fluorescence character-
ise the UV/Vis spectrum of dibenzocoronenebis(dicarbox-
imide) 5. The optical properties are in good agreement with
the results of the semiempirical calculations. Insoluble deriv-
atives of 5 may be useful as new stable yellow pigments.
Further, one can envision their use in optoelectronic devices
such as field effect transistors, as good phase forming ability
is expected when decorated with long alkyl chains.[27] The
UV/Vis spectrum of dinaphthoquaterrylenebis(dicarboxi-
mide) 6 is characterised by the intensive absorption between
600 and 750 nm and a bluish-green colour in a solution. The
intensive fluorescence with the quantum yield of 40%
makes the new dye 6 useful as a red absorbing fluorophore
that possesses an extremely high photostability. The latter
makes it a promising dye for biolabelling and multichromo-
phoric systems for energy and electron transfer.
Figure 4. Molecular orbitals (PM3) of coronenebis(dicarboximide) (CDI),
coronene, perylenebis(dicarboximide) (PDI), dibenzocoronenebis(dicar-
boximide) (DBCDI) and dinaphthoquaterrylene bis(dicarboximide)
(DNQDI). Abbreviations for molecular orbitals (MO): HOMO=highest
occupied, NHOMO=next highest occupied, LUMO=lowest unoccu-
pied, NLUMO=next lowest unoccupied.
LUMO.[25] The theoretical calculations clearly reproduce the
hypsochromically shifted absorption, as the energy value of
the HOMO of CDI is lower relative to PDI, whereas the
Experimental Section
LUMO energy is increased, thus leading to
HOMO–LUMO gap.
a larger
General: Melting points were performed on a Büchi melting point appa-
1
ratus and are not corrected. H NMR and 13C NMR spectra were record-
ed in deuterated solvents on a Bruker AMX 300 and Bruker Avance 700,
with the residual proton resonance or the carbon signal of the solvent as
the internal standard. For 13C J-modulated spin-echo NMR measure-
ments, the abbreviations q and t represent quaternary carbons, CH2, and
CH3, CH groups, respectively. Infrared spectra were obtained on a Nico-
The calculated orbitals of the new dibenzocoronene and
dinaphthoquaterrylene derivatives (Figure 4) are similar to
those of the corresponding rylenes, showing a similar UV
absorption behaviour with only one main band. The deter-
mined HOMO–LUMO band gaps of 5 and 6 are slightly in-
creased relative to the perylene- and quaterrylenebis(dicar-
boximide)s, respectively, causing a hypsochromic shift in ab-
sorption, in good agreement with the experimental data.
let FT-IR 320. UV/Vis spectra were recorded on
a Perkin–Elmer
Lambda 40 spectrophotometer at room temperature. Fluorescence spec-
tra were recorded on a Spex Fluorolog 3 spectrometer. Fluorescence
quantum yields were determined by the relative method using the follow-
ing compounds as references: acridine yellow for dibenzoCDI 5 and
Rhodamine 800[28] for dinaphtoQDI 6. FD mass spectra were obtained
on a VG Instruments ZAB 2-SE-FPD. The elemental analyses were car-
ried out by the Microanalytical Laboratory of Johannes Gutenberg Uni-
versity, Mainz. 1,7-Dibromo-3,4:9,10-perylene tetracarboxdianhydride (7)
and N,N’-bis(2,6-diisopropylphenyl)quaterrylene-3,4:13,14-bis(dicarbox-
Photochemical stabilities: The photochemical stability of the
dibenzoCDI 5 is much higher than that of CDI 4: the ab-
sorption of 4 in the chloroform under UV irradiation[26]
dropped to 34% of its initial value after 10 h. The benzan-
nulated derivatives 5 still showed absorption of 76% under
the same conditions. Presumably, the bonds between the 5-
and 6-positions and the 11- and 12-positions in the corone-
nebis(dicarboximide) 4 have some double bond character,
which makes them less stable. These bonds are part of other
aromatic p systems in the dibenzocoronenebis(dicarboxi-
mide) 5 (Figure 4), leading to the higher stability. The pho-
tochemical stability of the core-extended QDI 6 is even
higher than that for dibenzoCDI 5. The absorption spectrum
of 6 remained the same after 12h of UV irradiation. [26]
imide) (1c) were provided by the BASF AG. All other starting materials
were purchased from Aldrich, Acros, ABCR, or Lancaster, and used as
received.
N,N’-Bis(2,6-diisopropylphenyl)-1,7-bis(2-bromophenyl)perylene-3,4:9,10-
bis(dicarboximide) (9a): A Schlenk flask was charged with compound 8a
(1.00 g, 1.15 mmol), 2-bromophenylboronic acid (500 mg, 2.49 mmol), tet-
rakis(triphenylphosphine)palladium(0) (150 mg, 0.130 mmol), toluene
(75 mL), ethanol (5 mL) and a 2m solution of potassium carbonate
(25 mL) under argon. The mixture was heated to 758C with vigorous stir-
ring for 12h. It was then cooled to room temperature and the organic
phase separated and washed twice with water. After drying with magnesi-
um sulphate, the solvent was removed in vacuo. The crude product was
dissolved in methylene chloride and filtered over silica gel. Evaporation
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K. Müllen et al.
of the solvent gave 620 mg (53%) of red crude product, which was used
without further purification.
4H), 1.55–1.30 (m, 40H), 0.84 ppm (t, 3J=6.9 Hz, 12H); 13C NMR
(125 MHz, C2D2Cl4, 1008C, TMS): d=165.00 (C=O), 129.59, 129.17,
128.37, 124.67, 124.14, 123.86, 122.51, 122.35, 106.90, 55.67 (CH), 33.08
(CH2), 32.06 (CH2), 29.96 (CH2), 29.44 (CH2), 27.56 (CH2), 22.77 (CH2),
14.16 ppm (CH3); IR (KBr): n˜ =2956, 2926, 2854, 1703, 1660, 1606, 1437,
1315, 810, 741 cmÀ1; UV/Vis (CHCl3): lmax (e)=334 (42000), 350 (78000),
431 (12000), 459 (33000), 493 nm (65000 mÀ1 cmÀ1); MS (8 kV): m/z (%):
957.6 (100) [M+].
N,N’-Bis(2,6-diisopropylphenyl)-5,6:11,12-dibenzocoronene-2,3:8,9-bis(di-
carboximide)
(15 mg, 0.021 mmol) was added to a solution of compound 9a (100 mg,
0.098 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (60 mg, 0.39 mmol)
(5a):
dichloridobis(triphenylphosphine)palladium(II)
AHCTREUNG
in dry dimethylacetamide (3 mL) under argon. The mixture was heated
to 1608C with stirring for 24 h, was cooled to room temperature and was
diluted with methylene chloride. The mixture was washed twice with
water and dried over magnesium sulfate and the solvent removed in
vacuo. The crude product was purified by column chromatography (silica
gel, methylene chloride) to yield 40 mg (46%) of a yellow solid. M.p.
N,N’-Bis
This compound was synthesised as described in literature.[18]
N,N’-Bis(n-octyl)-5,6:11,12-dibenzocoronene-2,3:8,9-bis(dicarboximide)
(5c): Compound 8c (260 mg, 0.34 mmol), [Pd(dba)2] (50 mg), P(o-tolyl)3
A
AHCTREUNG
A
ACHTREUNG
1
2408C (decomp); H NMR (700 MHz, C2D2Cl4, 2 08C, TMS): d=10.66 (s,
(35 mg), 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (400 mg) and
CsF (300 mg) were stirred at 958C in the mixture of toluene (40 mL) and
acetonitrile (4 mL) for 24 h under argon. The resulting mixture was al-
lowed to stand overnight at room temperature. The precipitate formed
was filtered, rinsed with methanol and crystallised from toluene to yield
4H), 9.56 (m, 4H), 8.22 (m, 4H), 7.53 (dd, 3J=7.7 Hz, 4J=2.1 Hz, 2H),
7.40 (d, 3J=8.5 Hz, 4H), 2.99 (sept, 3J=6.8 Hz, 4H), 1.26 ppm (d, 3J=
6.8 Hz, 24H); 13C NMR (J-modulated spin-echo; 175 MHz, C2D2Cl4,
1008C, TMS): d=164.77 (q, C=O), 146.39 (q), 131.67 (q), 130.12(q),
129.76 (t), 129.68 (t), 129.35 (q), 125.24 (q), 125.22 (q), 124.96 (t), 124.87
(t), 124.31 (t), 124.01 (q), 122.72 (q), 29.73 (CH), 24.29 ppm (CH3); IR
(KBr): n˜ =2962, 2927, 2869, 1698, 1663, 1655, 1581, 1541, 1459, 1363,
1351, 1278, 1214, 1175 cmÀ1; UV/Vis (CHCl3): lmax (e)=432(10000), 460
(32000), 494 nm (66000 mÀ1 cmÀ1); MS (8 kV): m/z (%): 859.2(100) [ M+
], 429.3 (23) [M2+]; elemental analysis calcd (%) for C60H46N2O4: C
83.89, H 5.40, N 3.26; found: C, 83.66; H, 5.38; N, 3.12.
205 mg (80%) of
a
yellow solid. M.p. 3468C (decomp); 1H NMR
(500 MHz, C2D2Cl4, 1008C, TMS): d=9.62(s, 4H), 8.90 (m, 4H), 8.01
(m, 4H), 4.31 (t, 3J=7.5 Hz, 4H), 1.61–1.57 (m, 4H), 1.53–1.47 (m, 4H),
1.42–1.25 (m, 16H), 0.93 ppm (t, 3J=6.9 Hz, 6H); IR (KBr): n=2955,
2922, 2846, 1697, 1661, 1607, 1440, 1326, 1255, 811, 742 cmÀ1; UV/Vis
(chlorobenzene, 1008C): lmax (e)=337 (32500), 353 (64100), 433 (8100),
460 (24000), 492 nm (45800mÀ1 cmÀ1); MS (MALDI-TOF): m/z (%): 763
(100) [M+]; elemental analysis calcd (%) for C52H46N2O4: C 81.86, H
6.08, N, 3.67; found: C 81.66, H 6.18, N 3.58.
N,N’-Bis(1-heptyloctyl)-1,7-dibromoperylene-3,4:9,10-bis(dicarboximide)
(8b): The mixture of compound 7 (500 mg, 0.909 mmol) and 1-heptyloc-
tylamine (750 mg, 3.298 mmol) in N-methylpyrrolidone (NMP; 50 mL)
was stirred at 1508C. After 4 h the mixture was allowed to cool down to
room temperature and was then poured into diluted hydrochloric acid
(400 mL). The precipitate was collected by filtration, was washed with
water and methanol several times and was dried under reduced pressure
at 808C. The crude product was purified by column chromatography
(silica gel, petrol ether/methylene chloride 3:2) to yield 340 mg (39%) of
a red wax. 1H NMR (300 MHz, CD2Cl2, 2 08C, TMS): d=9.53 (s, 1H),
9.50 (s, 1H), 8.89 (brs, 2H), 8.66 (d, 3J=7.2Hz, 2H), 5.20–5.12 (m, 2H),
2.25–2.20 (m, 4H), 1.86–1.80 (m, 4H), 1.28–1.22 (m, 40H), 0.85–0.81 ppm
(m, 12H); 13C NMR (J-modulated spin-echo; 175 MHz, C2D2Cl4, 1008C,
TMS): d=162.55 (C=O), 138.21, 137.13, 132.86, 132.66, 131.52, 130.10,
129.28, 128.48, 127.18, 120.61, 54.75 (CH), 41.08 (CH2), 31.77 (CH2),
29.44 (CH2), 29.18 (CH2), 26.85 (CH2), 22.59 (CH2), 13.79 ppm (CH3); IR
(KBr): n˜ =2956, 2925, 2854, 1703, 1660, 1589, 1381, 1329, 1240, 810,
N,N’-Bis-(N-2,6-diisopropylphenyl)-1,6,8(9),11,16,18-hexabromoquaterry-
lene-3,4:13,14-bis(dicarboximide) (10): Compound 1c (3 g, 3.0 mmol) and
bromine (65 mL, 1.26 mol) was stirred in chloroform (1.3 L) at 558C for
60 h. The reaction mixture was cooled to room temperature and added to
a vigorously stirred solution of KOH (15 g) and Na2SO3 (15 g) in water
(2L). Then Na 2SO3 was added to the stirred solution until the aqueous
layer became colourless. The organic layer was separated, dried with an-
hydrous sodium sulfate and evaporated. The residue was purified by the
column chromatography on silica gel with dichloromethane as eluent to
give 10 as
a
green powder (3.6 g, 84%). M.p. >3508C; 1H NMR
(250 MHz, CD2Cl2, 2 08C, TMS): d=9.71 (s, 1H) 9,68 (s, 1H), 9.53 (d,
3J=8.7 Hz, 1H), 9.48 (d, 3J=8.7 Hz, 1H), 9.38 (d, J=8.75 Hz, 1H), 9.33
(d, 3J=8.7 Hz, 1H), 9.00 (s, 1H), 8.99 (s, 1H), 8.89 (s, 1H), 8.92(s, 1H),
7.54 (t, 3J=8.2Hz, 2H), 7.38 (d, 3J=7.8 Hz, 4H), 2.77 (sept, 3J=6.9 Hz,
4H), 1.18 ppm (d, 3J=6.8 Hz, 24H); 13C NMR (67 MHz, CD2Cl2, 2 08C,
TMS): d=161.7, 161.4, 145.0, 133.5, 131.8, 129.8, 129.5, 129.1, 128.6,
128.5, 128.4, 128.3, 126.1, 125.5, 121.5, 120.9, 119.6, 119.5, 28.5, 23.1 ppm;
IR (KBr): n˜ =2961, 2927, 2867, 1717, 1713, 1705, 1674, 1590, 1573, 1468,
1386, 1348, 1233, 1197, 1172, 1152, 1051, 842, 815, 794, 724 cmÀ1; UV/Vis
(toluene): lmax (e)=752(113000), 686 nm (59300 mÀ1 cmÀ1); MS (8 kV):
m/z (%): 1431.6 (100) [M+]; elemental analysis calcd (%) for
C68H44Br6N2O4: C 56.71, H 3.10, N 1.96; found: C 56.07, H 3.13, N 1.99.
748 cmÀ1
; UV/Vis (CHCl3): lmax (e)=390 (6000), 460 (15000), 490
(37000), 526 nm (55000mÀ1 cmÀ1); MS (FD, 8 kV) : m/z (%): 971.3 (100)
[M+].
N,N’-Bis(1-heptyloctyl)-1,7-bis(2-bromophenyl)perylene-3,4:9,10-bis(di-
carboximide) (9b): A Schlenk flask was charged with compound 8b
(600 mg, 0.619 mmol), 2-bromophenylboronic acid (250 mg, 1.238 mmol),
tetrakis(triphenylphosphine)palladium(0) (72mg, 0.062mmol), toluene
(50 mL), ethanol (2mL) and a 2 m solution of potassium carbonate
(25 mL) under argon. The mixture was heated to 758C with vigorous stir-
ring for two days. It was then cooled to room temperature and the organ-
ic phase separated and washed twice with water. After drying with mag-
nesium sulphate, the solvent was removed in vacuo. The crude product
was dissolved in petrol ether/methylene chloride (3:2) and filtered over
silica gel. Evaporation of the solvent gave 600 mg (87%) of red crude
product, which was used without further purification.
N,N’-Bis-(N-2,6-diisopropylphenyl)-1,6,11,16-tetrakis[4-(1,1,3,3-tetrameth-
ylbutyl)phenoxy]-8(9),18-dibromoquaterrylene-3,4:13,14-bis(dicarbox-
imide) (11): Compound 10 (1.43 g, 1 mmol), tert-octylphenol (0.845 g,
4 mmol) and K2CO3 (0.3 g, 2.2 mmol) were suspended in NMP (150 mL)
in a 250 mL Schlenk flask and flushed with argon. The mixture was
stirred at 1108C for 48 h under argon. After cooling to room tempera-
ture, the mixture was poured into a mixture of 6m HCl (100 mL) and ice
(200 g). The green precipitate was filtered, rinsed with water and dried
under vacuum. Compound 11 was isolated after column chromatography
on silica gel with toluene as eluent. Yield 1.44 g (85%); M.p. >3508C;
1H NMR (500 MHz, CD2Cl2, 2 08C, TMS): d=9.78 (s, 3H), 9.57 (d, 3J=
8.95 Hz, 2H), 9.18 (d, 3J=8.80 Hz, 2H), 8.23 (s, 4H), 7.50 (m, 9H) 7.33
(d, 3J=7.74 Hz, 4H), 7.16 (d, 3J=8.65 Hz, 8H), 2.50 (sept, 3J=6.80 Hz,
4H), 1.70 (s, 8H), 1.35 (s, 24H), 1.10 (d, 3J=6.79 Hz, 24H), 0.70 ppm (s,
36H); 13C NMR (125 MHz, CD2Cl2, 2 80C, TMS): d=163.47, 155.61,
154.92, 153.74, 153.53, 153.39, 153.29, 147.42, 147.25, 147.15, 146.48,
135.95, 131.55, 120.58, 130.13, 129.81, 129.69, 129.09, 128.61, 128.58,
128.34, 127.97, 127.84, 126.00, 125.55, 124.46, 123.68, 123.40, 122.84,
122.51, 120.62, 119.27, 119.17, 118.73, 118.60, 118.55, 57.50, 38.74, 38.72,
32.65, 31.91, 31.71, 29.51, 24.13 ppm; IR (KBr): n˜ =2957, 1707, 1670,
N,N’-Bis(1-heptyloctyl)-5,6:11,12-dibenzocoronene-2,3:8,9-bis(dicarbox-
imide) (5b): Dichloridobis(triphenylphosphine)palladium(II) (10 mg,
0.014 mmol) was added to
0.071 mmol) and 1,8-diazabicyclo
a
solution of compound 9b (80 mg,
[5.4.0]undec-7-ene (43 mg, 0.284 mmol)
AHCTREUNG
in dry dimethylacetamide (3 mL) under argon. The mixture was heated
to 1608C with stirring for 18 h, cooled to room temperature and diluted
with methylene chloride. The mixture was washed twice with water and
dried over magnesium sulfate and the solvent removed in vacuo. The
crude product was purified by column chromatography (silica gel, tolu-
ene) to yield 44 mg (65%) of a yellow solid. M.p. >3508C; 1H NMR
(300 MHz, C2D2Cl4, 1008C, TMS): d=9.78 (s, 4H), 9.06 (m, 4H), 8.16
(m, 4H), 5.36 (quint, 3J=6.7 Hz, 2H), 2.54–2.44 (m, 4H), 2.23–2.14 (m,
6560
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ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 6555 – 6561

Dyes/Pigments
FULL PAPER
1595, 1503, 1334, 1210 cmÀ1; UV/Vis (toluene): lmax (e)=758 (157900),
688 nm (77000mÀ1 cmÀ1); MS: m/z (%): 1934.2(100) [ M+]; elemental
analysis calcd (%) for C124H128Br2N2O8: C 83.84, H 7.38, N 1.58; found: C
83.67, H 7.29, N 1.50.
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N,N’-Bis-(N-2,6-diisopropylphenyl)-1,6,11,16-tetrakis[4-(1,1,3,3-tetrameth-
ylbutyl)phenoxy]-8,9:18,19-dinaphthoquaterrylene-3,4:13,14-bis(dicarbox-
imide) (6): Compound 11 (1,94 g, 1 mmol), [Pd
N
N
tolyl)3 (30 mg), 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (1.5 g)
and CsF (460 mg) were stirred at 958C in the mixture of toluene (90 mL)
and acetonitrile (10 mL) for 48 h under argon. The resulting mixture was
cooled and washed with water. The organic layer was separated, evapo-
rated under vacuum and purified by column chromatography on silica gel
with toluene as eluent. Yield 0,89 g (46%); M.p. >3508C; 1H NMR
(500 MHz, C2D2Cl4, 1008C, TMS): d=11.18 (s, 4H), 8.74 (brs, 4H), 8.54
(s, 4H), 7.59 (brs, 4H), 7.43–7.45 (m, 10H) 7.28–7.30 (m, 12H), 2.84
(sept, 3J=6.68 Hz, 4H), 1.71 (s, 8H), 1.38 (s, 24H), 1.10 (d, 3J=6.71 Hz,
24H), 0.69 ppm (s, 36H); 13C NMR (175 MHz, C2D2Cl4, 1008C, TMS):
d=163.37, 154.35, 154.01, 147.03, 146.18, 132.47, 131.50, 129.83, 129.51,
128.40, 128.20, 127.94, 127.68, 126.80, 125.69, 125.27, 124.18, 124.15,
123.999, 123.96, 123.91, 122.93, 122.55, 118.02, 57.59, 38.70, 32.44, 31.98,
31.63, 29.56, 24.22 ppm; IR (KBr): n˜ =2958, 2919, 2863, 1707, 1663, 1590,
1501, 1355, 1311, 1503, 1205, 1160 cmÀ1; UV/Vis (toluene): lmax (e)=700
(142900), 638 (62800), 589 (16000), 411 (31000), 389 nm
(21500mÀ1 cmÀ1); MS (FD): m/z (%): 1926 (100) [M+]; elemental analy-
sis calcd (%) for C136H134N2O8: C 84.88, H 7.02, N, 1.46; found: C 84.74,
H 7.11, N 1.50.
Acknowledgements
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Financial support of this work by the BASF AG and Deutsche For-
schungsgemeinschaft (project SFB 625) is gratefully acknowledged. S.M.
thanks the Fonds der chemischen Industrie and the Bundesministerium
für Bildung und Forschung for financial support.
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Received: April 4, 2007
Published online: July 5, 2007
Chem. Eur. J. 2007, 13, 6555 – 6561
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6561