Synthesis and modification of terrylenediimides as high-performance fluorescent dyes

Article abstract of DOI:10.1002/chem.200401177

Two new synthetic approaches to terrylenediimides, highly photostable fluorescent dyes, are described. For the first time terrylenediimide has been synthesised in a straightforward procedure that makes large quantities available. The second route includes an efficient cross-coupling reaction followed by a cyclodehy-drogenation. Monofunctionalisation of the imide structure allows terrylenediimides now to be coupled with a variety of compounds, for example, by Suzuki cross-coupling, which can lead to an array of terrylenediimides with new functional groups such as hydroxy, amino, or carboxy groups needed to link up with other molecules. The functionalisation in the bay region is used to tune the properties of terrylenediimides and extend the range of applications, for example, by introducing water solubility. These tetrasubstituted terrylenediimides offer, depending on the substituents used, exciting features such as good solubility in common organic solvents, water solubility, or NIR absorption.

Full text of DOI:10.1002/chem.200401177

FULL PAPER
Synthesis and Modification of Terrylenediimides as High-Performance
Fluorescent Dyes
Fabian Nolde, Jianqiang Qu, Christopher Kohl, Neil G. Pschirer, Erik Reuther, and
Klaus Mꢀllen*[a]
Abstract: Two new synthetic ap-
proaches to terrylenediimides, highly
photostable fluorescent dyes, are de-
scribed. For the first time terrylenedi-
ides now to be coupled with a variety
of compounds, for example, by Suzuki
cross-coupling, which can lead to an
array of terrylenediimides with new
functional groups such as hydroxy,
amino, or carboxy groups needed to
link up with other molecules. The func-
tionalisation in the bay region is used
to tune the properties of terrylenedi-
imides and extend the range of applica-
tions, for example, by introducing
water solubility. These tetrasubstituted
terrylenediimides offer, depending on
the substituents used, exciting features
such as good solubility in common or-
ganic solvents, water solubility, or NIR
absorption.
imide has been synthesised in
a
straightforward procedure that makes
large quantities available. The second
route includes an efficient cross-cou-
pling reaction followed by a cyclodehy-
drogenation. Monofunctionalisation of
the imide structure allows terrylenediim-
À
Keywords: C C coupling
pigments · fluorescence · terrylene-
· dyes/
diimides
Introduction
in the red and deep red spectral region of the electromag-
netic spectrum is rather limited.[10] A great advantage of this
spectral region is that inexpensive and effective excitation
sources such as the HeNe laser (633 nm), krypton-ion laser
(647, 676 nm) and common diode lasers are available, which
is important for fluorescent labels.[11] In addition to the pho-
tophysical properties such as high extinction coefficients and
photochemical stability, the negligible population of the trip-
let bottleneck, low photobleaching efficiency at room tem-
perature, and weak electron–phonon coupling at low tem-
perature qualify terrylenediimide 3 as an ideal chromophore
for single-molecule spectroscopy.[12] With single-molecule
spectroscopy experiments, it is also possible to excite and
detect the zero-phonon line of single terrylenediimide mole-
cules, which is only possible with exceptionally photostable
systems.[13] Terryleneimides have been used in biomimetic
models of plant photosystems,[14] bichromophores,[15] and
light-harvesting dyads[16] and triads.[17]
Our previously published synthesis of terryleneimide,
however, suffered from the following problems:[7] 1) the use
of toxic stannyl compounds as intermediates, 2) long reac-
tion times (three days for transformation of bromide 7 into
stannyl derivative 6; four days for the subsequent Stille cou-
pling), 3) the use of molten KOH as base in the final cyclo-
dehydrogenation, which excludes the synthesis of terrylene-
imides with base-labile substituents at the N-imide position
and causes corrosion of the reaction vessel, 4) limited access
Stable, highly fluorescent perylene-3,4:9,10-tetracarboxdi-
imides of type 1 are widely used as dyes or pigments, de-
pending on the substituent R at the N-imide position
(Scheme 1). They are suitable for demanding applications
such as modern reprographics,[1] fluorescence light collec-
tors,[2] photovoltaic devices,[3] dye lasers,[4] light-emitting
diodes (LEDs)[5] and molecular switches.[6] By extending the
core p-conjugated system, we have synthesised the higher
homologues of perylenediimide 2, that is, terrylenediimide
3[7] and quaterrylenediimide 4.[8] The absorption maxima of
the deep blue terrylenediimides 3 are shifted bathochromi-
cally in comparison to perylenediimide 2. Terrylenediimides
3 exhibit brilliant colour, high extinction coefficients, high
fluorescence quantum yields of 90%,[7] and high thermal,
chemical, and photochemical stabilities, which are generally
required for practical use.[9] The number of organic com-
pounds showing intense fluorescence like terrylenediimide
[a] F. Nolde, Dr. J. Qu, Dr. C. Kohl, Dr. N. G. Pschirer, Dr. E. Reuther,
Prof. Dr. K. Mꢀllen
Max-Planck-Institute for Polymer Research
Ackermannweg 10, 55128 Mainz (Germany)
Fax : (+49)6131-379-350
E-mail: muellen@mpip-mainz.mpg.de
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Scheme 1. Chemical structures of rylenediimides.
to the soluble disubstituted terrylenediimide 5, and 5) the
unavailability of functional groups for further reactions.
Two new strategies are now available to improve the es-
tablished synthesis of symmetrical and unsymmetrical terry-
lenediimides[7,18] that avoid the use of toxic organostannanes
and provide higher overall yields.[19] Both routes also offer
the important possibility of controlled monofunctionalisa-
tion of the imide structure of terrylenediimides. Although
many monofunctionalised perylenediimides have been de-
scribed, monofunctionalisation methods for the higher ho-
mologues, terrylenediimides, are hithertho unknown. By
starting from tetrabromoterrylenedicarboximide 19, the syn-
thesis of a series of terrylenediimides in which it is possible
to significantly increase the solubility (Table 1), to introduce
water solubility or to obtain NIR-absorbing dye is accom-
plished.
ester 8 with 4-bromonaphthalenedicarboximide 9a and 9b
gives the naphthylperylene derivatives 10a and 10b in good
yields (10a 85%, 10b 90%). Terrylenediimide precursors
10a and 10b are then cyclised by using K2CO3 as base in
ethanolamine. After isolation and purification by column
chromatography, 3a and 3b are both obtained in 95% yield.
The synthesis of boronic acids or esters normally involves
the reaction of organolithium reagents with trialkyl borates.
This method is not applicable here, since the imide structure
is sensitive to organolithium compounds. We therefore used
the method reported by Miyaura et al., which transforms
aryl halides directly into boronic esters even in the presence
of functional groups such as esters, ketones and nitro
groups.[22] Under these conditions, debrominated and homo-
coupled derivates of 7 are obtained as minor by-products,
and hence column chromatography is required for purifica-
tion.
Another advantage of Suzuki cross-coupling of boronic
ester 8 and 9a is that it proceeds considerably faster (16 h)
than the previous palladium-catalysed Stille coupling of or-
ganostannane 6 and 9a (96 h). The synthesis of the terryl-
enediimide precursors 10a and 10b can also be carried out
by using the analogous boronic ester of 4-bromonaphtha-
lenedicarboximides 9a and 9b and 9-bromo-perylenedicar-
boximide 7.
Table 1. Solubility of terrylenediimides 3, 19 and 20a in CH2Cl2 at room
temperature.
Compound
3
19
20a
Solubility [mgmLÀ1
]
1.5
18
> 180
Results and Discussion
The final cyclodehydrogenation step of this protocol is
carried out under very mild conditions.[23,24] In contrast to
the cyclisation with molten KOH, the cyclisation of 10a and
10b with K2CO3 as base in ethanolamine gives almost quan-
titative yields. The use of an oxidative alkali melt has anoth-
er drawback, because unlike the bulky N-substituents of
naphthylperylene derivative 10a, the cyclohexyl substituent
of 10b can be saponified with such a strong base. The for-
mation of terrylenediimides with base-labile N-substituents
can therefore be accomplished only under very mild condi-
The first new synthetic route (Scheme 2) to terrylenedi-
imides is similar to the previous one, but in all three steps
major improvements were made. Here, the toxic stannyl de-
rivative 6 is replaced with a boronic ester 8, whose synthesis
has recently been described.[20] With bis(pinacolato)diboron
and [PdCl2(dppf)] (dppf=1,1’-bis(diphenylphosphino)ferro-
cene) it is possible to convert 9-bromoperylenedicarbox-
imide 7 to the corresponding boronic ester 8 in 75% yield.
In a Pd-catalysed Suzuki reaction,[21] coupling of boronic
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Terrylenediimide Fluorescent Dyes
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Scheme 2. Synthesis of 3a, 3b and 14. a) [Pd(PPh3)4], K2CO3/H2O, toluene, 808C, 16 h (10a 85%, 10b 90%); b) ethanolamine, K2CO3, 1208C, 3 h, 95 %;
c) [Pd(PPh3)4], K2CO3/H2O, toluene, 808C, 15 h, 80%; d) 4-bromo-2,6-diisopropylaniline, propionic acid, 1508C, 16 h, 38%; e) ethanolamine, K2CO3,
1608C, 3 h, 90%.
tions. It is now possible to per-
form the saponification of the
cyclohexyl substituent of 3b,
which is unwanted in the final
cyclodehydrogenation, with
a
strong base like KOH to gain
terrylenemonoanhydridemono-
imide 3c, which provides terryl-
enemonoimide 3d after decar-
boxylation.[25] This has potential
as a starting material for the
synthesis of the higher homo-
logues of 2–4 with even larger p
systems.
Scheme 3. Synthesis of 3 and 18a. a) Diazabicyclo[4.3.0]non-5-ene, tBuONa, diglyme, 1308C, 3 h, 42%;
b) diazabicyclo[4.3.0]non-5-ene, tBuONa, diglyme, 1308C, 2 h, 36%.
After isolation and purifica-
tion by column chromatogra-
phy, 3a is obtained in an overall
yield of 63%. This new synthetic route (Scheme 2) thus
gives a 13% increase in overall yield compared to the previ-
ous procedures and avoids toxic organostannanes like 6.
The second route (Scheme 3) for terrylenediimide 3 is
even simpler because it utilizes a one-pot procedure which
is reminiscent of the direct coupling reactions of 1,8-naph-
thalenedicarboximides affording the corresponding peryl-
enediimide dyes.[19,26,27] Heating a mixture of perylenedi-
carboximide 15, naphthalenedicarboximide 16, 1,5-
diazabicyclo[4.3.0]non-5-ene (DBN) and tBuONa in diglyme
delivers terrylenediimide 3.
In addition to the enhanced multistep synthesis involving
column chromatography we are looking for a short route
usable on a very large scale. Perylenediimides[19] and quater-
rylenediimides,[28] the lower and higher homologues of terry-
lenediimides, can be synthesised by base-promoted homo-
coupling of naphthalenedicarboximide or perylenedicarbox-
imide, respectively. The obvious synthesis of symmetric ter-
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K. Mꢀllen et al.
rylenediimide 3 in this kind of one-pot base-promoted reac-
tion would depend on heterocoupling of perylenedicarbox-
imide 15 and naphthalenedicarboximide 16. In principle,
under these reaction conditions three combinations—two
homocouplings and the desired heterocoupling—could read-
ily form diimides. To favour the heterocoupling and suppress
the formation of the homocoupling product quaterrylenedi-
imide 4, which can not be easily separated, a fourfold excess
of naphthalenedicarboximide 16 is used to provide terryl-
enediimide 3.
By using KOH/glucose/ethanol in the heterocoupling only
perylenediimide 2 is obtained. The improved cyclodehydro-
genation conditions of the multistep route (K2CO3, ethanol-
amine; Scheme 2) give terrylenediimide 3 and the unwanted
byproduct quaterrylenediimide 4. Owing to the low yield of
terrylenediimide 3 and the formation of quaterrylenediimide
4, these conditions are not suitable. The tBuONa/DBN pair
gives rise to terrylenediimide 3 without the formation of
quaterrylenediimide 4 after 3 h at 1308C in diglyme under
argon. The only byproduct, perylenediimide 2, and the re-
maining starting materials can be removed by washing with
ethanol because of their good solubility. Terrylenediimide 3
is finally recrystallised from ethanol/chloroform to give an
overall yield of 42% with >95% purity. The time-consum-
ing chromatographic purification and bromination of peryl-
enemonoimide 15 characteristic of the multistep route can
now be avoided and scale-up (>100 g) becomes easily possi-
ble.
The base-promoted one-pot reaction is also the simplest
monofunctionalisation method for terrylenediimides. The
use of a perylenedicarboximide and a naphthalenedicarbox-
imide with different substituents in the imide structures
afford an asymmetric terrylenediimide in the one-pot syn-
thesis (Scheme 3). Monocarboxy-functionalised terrylenedi-
imide 18a was synthesised by using N-(5-carboxypentyl)-
naphthalenedicarboximide 17a in place of nonfunctionalised
naphthalenedicarboximide 16 under the same conditions
(tBuONa/DBN, diglyme) used in the one-pot synthesis of
terrylenediimide 2. The reaction mixture of the coupling re-
action is poured into a small amount of water to obtain the
sodium salt of monocarboxyl-substituted terrylenediimide
18a. A very convenient way of purifying the sodium salt is
by washing away all by-products and all starting materials
with chloroform. The sodium salt is insoluble in nonpolar
solvents (e.g., chloroform, as used here). The dark blue pre-
cipitate is then redissolved in methanol and acidified with
hydrochloric acid to give the desired pure monocarboxy-
functionalised terrylenediimide 18a in 36% yield.
conditions boronic ester 8 couples with 4-bromonaphthal-
enedicarboxanhydride 11 to give anhydride 12 in 80% yield.
The naphthylperylene derivative 13 is obtained by conden-
sation of 12 with a monobromo-functionalised amine in
38% yield. The ring closure of 13, which is carried out with
K2CO3 in ethanolamine, affords terrylenediimide 14 under
mild conditions in 90% yield.
Selective cross-coupling of boronic ester 8 with a 4-bro-
monaphthalenedicarboximide with a bromo substituent on
the aryl group at the N-imide position is not possible.
Hence, the bromo substituent must be introduced later.
With 4-bromonaphthalenedicarboxanhydride 11 and cataly-
sis by [Pd(PPh3)4], boronic ester 8 is coupled to the naph-
thylperylene derivative 12, which allows the introduction of
a bromo-functionalised aniline or other secondary amines in
the imide structure. Monofunctionalisation is achieved by
imidisation of anhydride 12 with a bromo-containing amino
substituent. 4-Bromo-2,6-diisopropylaniline was used to also
improve the solubility and stability of naphthylperylene de-
rivative 13, due to the bulky ortho-alkyl substituents. The
reason for the moderate yield is decomposition of anhydride
12 at 1508C.[29] With K2CO3 as base in ethanolamine, the cy-
clodehydrogenation of 13 completes the synthesis of the cor-
responding terrylenediimide with one para-bromo substitu-
ent 14 in excellent yield.
Tetrabromoterrylenediimide 19, whose synthesis has re-
cently been described,[20] creates numerous possibilities for
the functionalization of terrylenediimide (Scheme 4), since
19 is susceptible to reactions with nucleophiles at the bromi-
nated positions.[2] The phenoxylation of 19 with tert-octyl-
phenol gives the corresponding tetrasubstituted terrylenedi-
carboximide 20a in 86% yield. The substitution under basic
conditions of the four bromine atoms of 19 with phenol pro-
duces 20c in 90% yield. Further, this terrylenediimide can
be sulfonated with concentrated sulfuric acid at room tem-
perature to afford 21. The reaction of piperidine with 19 at
858C forms the terrylenediimide with four piperidyl sub-
stituents 20d in 34% yield.
Perylenediimides can be halogenated in the bay region,[2,8]
and perylenemonoimides can be selectively brominated in
the 9-position.[8,30] Bromination of terrylenediimide 3 with
elemental bromine in chloroform at 608C with exclusion of
light gives the tetrabrominated terrylenediimide 19 as the
main product[20,25] No catalyst is required for this reaction.
The directing effect of the imide structures leads to selective
fourfold bromination in the 1-, 6-, 9- and 14-positions. How-
ever, bromination does not stop at tetrabromination, and
penta- and hexabrominated terrylenediimides are obtained
as minor by-products. Fortunately, penta- and hexabromina-
tion occur in the meta-positions of the imide phenyl rings
and not in the bay region or in the aliphatic side chains.
These by-products can be removed by column chromatogra-
phy with toluene or chloroform/ethanol.
À
The use of palladium-catalysed C C coupling reactions
(Stille, Suzuki etc.) makes a halogen-functionalised terryl-
enediimide an important intermediate (Scheme 3). The yield
of the monobrominated terrylenediimide derivative 18b is,
however, very low (<5%), since the bromo substituent does
not survive the strongly basic conditions of the base-promot-
ed one-pot reaction. Therefore, the synthetic route via the
boronic ester 8 was chosen to synthesise monobromo-func-
tionalised terrylenediimide 17b (Scheme 2). Under Suzuki
The introduction of bromine atoms leads to a significant
increase in solubility (Table 1), because of the distortion of
the terrylene skeletal structure of 19, and also changes the
spectral properties.[2] While the maxima of the absorption
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Terrylenediimide Fluorescent Dyes
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Scheme 4. Synthesis of 20a, 20d and 21. a) Br2, chloroform, reflux, 12 h, 75%; b) 20a: tert-octylphenol, K2CO3, N-methylpyrrolidone, 808C, 8 h, 86 %;
20c: phenol, K2CO3, N-methylpyrrolidone, 808C, 15 h, 90%; 20d: piperidine, 858C, 5 d, 34%; c) conc. H2SO4, RT, 15 h, 94%.
Figure 2. Absorption spectra of 19 (continuous line) and 20a (dashed
line) in toluene, and emission spectra of 19 (dotted line) and 20a (dash
dot line) in toluene.
Figure 1. Absorption (continuous line) and emission spectra (dotted line)
of 3 in toluene.
bands remain unaffected, the most intense emission band is
shifted bathochromically by 13 nm to 686 nm (Figure 1).
The bands in the emission spectrum of 19 are also broader
than the bands in the emission spectrum of 3.
also affords bluish green products instead of the blue terryl-
enediimides 3 and 19. The absorption wavelength depends
on the number of phenoxyl substituents. The maximum of
the diphenoxyl-substituted terrylenediimide 5 at 664 nm is
shifted hypsochromically compared to that of tetrasubstitut-
ed 20a by 11 nm. By varying the number of phenoxyl sub-
stituents on the terrylenediimides, it is possible to cover the
whole red and deep-red spectral region. The fluorescence
quantum yields of terrylenediimides 19 and 20a were deter-
mined relative to tetraphenylporphine, which has a known
fluorescence quantum yield (fF =0.10)[32] and absorbs at
similar wavelength. Compound 19 has a quantum yield of
64% (fF =0.64Æ0.1), and 20a one of 53% (fF =0.53Æ0.1).
The bromine atoms of terrylenediimide 19 can also be sub-
stituted by functional phenols like 4-iodophenol.[20] After
this tetrafunctionalisation, 20b can serve as a multifunction-
al core molecule for the synthesis of dendritic multichromo-
phores.
Several strategies are available to improve the solubility
of the ryleneimides. One option is the introduction of bulky
substituents such as 2,6-diisopropyl groups in the imide
structure. Phenoxyl substituents in the bay regions of the p
system also can be used to improve the solubility. The limit-
ed access to the soluble diphenoxy-substituted terrylenedi-
imide 5 is clearly an issue, since for many applications good
solubility in organic solvents is required.[31] The obvious way
to synthesise tetraphenoxy-substituted terrylenediimides,
which absorb and emit at longer wavelengths, is to phenoxy-
late tetrabrominated terrylenediimide 19. The bulky tert-oc-
tylphenoxy substituents of terrylenediimide 20a increase the
solubility dramatically (Table 1). The absorption bands and
emission band are shifted bathochromically because of sub-
stitution with four phenoxyl substituents (Figure 2), which
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K. Mꢀllen et al.
Even though terrylenediimides with four phenoxyl sub-
stituents such as 20a have good solubility in common organ-
ic solvents, they are insoluble in water and only slightly solu-
ble in polar solvents. For certain applications and environ-
mentally benign processes, good processability in water or
polar solvents is needed. One strategy to obtain solubility in
water is to introduce charged groups. Water-soluble peryl-
enediimides with four phenoxyl substituents bearing nega-
tively charged sulfonyl groups were reported recently.[33] The
same concept is used to obtain water-soluble terrylenedi-
imides. The para positions of the phenol substituents of 20d
are the expected the sites of sulfonation with sulfuric acid,
and indeed complete and selective conversion is obtained.
The purification of 21 is accomplished by slowly adding a
small amount of water to the reaction mixture, which direct-
ly induces precipitation of the product. After washing with
dichloromethane, water-soluble terrylenediimide 21, bearing
four sulfonyl groups, is isolated in 93% yield.
Direct substitution of the perylenediimide core can
change the chemical and optical properties.[34] Wasielewski
et al. reported that introduction of dialkylamino groups into
the bay regions leads to a large bathochromic shift of the
absorption bands.[35] The reaction of tetrabromoterrylenedi-
imide 19 with the electron-rich secondary cyclic amine pi-
peridine gives the first ever NIR-absorbing terrylenediimide
20d. The absorption maximum of the longest wavelength
absorption band of tetrapiperidinyl-substituted terrylenedi-
imide 20d at 819 nm is shifted bathochromically compared
to that of 19 by 168 nm (Figure 3), due the electron-donat-
bright blue. The absorption maximum of protonated 20d is
shifted hypsochromically by 197 nm (Figure 3). This solvent
effect on the charge transfer bands can be explained by pro-
tonation of the piperidinyl groups.[37]
Conclusion
With the current synthetic strategies—monofunctionalisa-
tion of the imide structure and additional functionalisation
in the bay region—the toolbox of terrylenediimide chemis-
try is notably enlarged. The nontoxic boronic ester 8 is a val-
uable intermediate in the new multistep synthesis of terryle-
nediimides. It provides access to monobromo-functionalised
terrylenediimide 14, which will be a useful in a broad variety
of palladium-catalysed cross-coupling reactions. Tetrabromo-
terrylenediimide 19 is used as a versatile building block for
the synthesis of a series of new terrylenediimides. To dra-
matically improve the handling of the dyes, terrylenediimide
20a with four phenoxyl substituents and good solubility in
common organic solvents and water-soluble terrylenedi-
imide 21 were synthesised. Substitution of the bromine
atoms of 19 with a cyclic amine afforded the first NIR-ab-
sorbing terrylenediimide 20d. Owing to the excellent redox
properties of the rylene dyes and NIR absorption, these
dyes could be candidates for organic photovoltaic cells and
field effect transistor (FET) devices. Furthermore the one-
pot synthesis of terrylenediimide offers an easy and attrac-
tive access to terrylene substrates from a commercial point
of view.
Experimental Section
General: The solvents used were of commercial grade. Perylenemono-
imide 15 was supplied by BASF AG. Compounds 8, 9a and 19 were pre-
pared as described in the literature.[7,20] Column chromathography was
1
preformed on silica gel (Geduran Si60, Merck). H and 13C NMR spectra
were recorded on Bruker Avanche 250, Bruker AMX 300, Bruker DRX
500 and Bruker Avanche 700. Infrared spectra were obtained on a Nico-
let FT IR 320. FD mass spectra were recorded with a VG-Instruments
ZAB 2-SE-FDP instrument. MALDI-TOF mass spectra were recorded
on a Bruker MALDI-TOF spectrometer. UV/Vis spectra were recorded
on a Perkin-Elmer Lambda 9, and fluorescence spectra on a SPEX Fluo-
rolog 3 spectrometer. The quantum yields were measured relative to tet-
raphenylporhine. Elemental analyses were preformed by the Department
of Chemistry and Pharmacy of the University of Mainz.
N-(Cyclohexyl)-4-bromonaphthalene-1,8-dicarboxiimide (9b): 4-Bromo-
1,8-naphthalic anhydride (35.0 g, 0.13 mol) and cyclohexylamine (28.0 g,
0.29 mol) were refluxed in ethanol (1 L) for 12 h. The reaction mixture
was cooled to room temperature. The resulting 9b was removed by filtra-
tion, washed with ethanol and dried under vacuum (45 g, 96%). M.p.
Figure 3. Absorption spectra of 20d in chloroform (dashed line) and in
sulfuric acid (continuous line), and absorption spectrum of 3 (dotted
line) in chloroform.
1
2658C; H NMR (250 MHz, C2D2Cl4, 258C): d=8.51 (d, J=8.47 Hz, 1H),
8.44 (d, J=8.47 Hz, 1H), 8.26 (d, J=8.17 Hz, 1H), 7.94 (d, J=7.82 Hz,
1H), 7.75 (t, J=7.8 Hz, 1H), 4.88 (m, 1H), 2.40 (m, 2H), 1.79 (m, 2H),
1.65 (m, 3H), 1.26 ppm (m, 3H); 13C NMR (62.5 MHz, C2D2Cl4, 258C):
d=165.07, 165.05, 133.99, 133.00, 132.20, 131.40, 130.99, 129.91, 129.25,
124.59, 123.74, 55.04, 30.21, 27.68, 26.58 ppm; IR (KBr pellet): n˜ =2919,
2846, 1703, 1655, 1585, 1362, 1258, 1233, 1186, 1109, 983, 910, 855, 779,
ing effect of the piperidinyl groups.[36] The charge transfer
also causes broadening and loss of the fine structure of the
absorption bands of 20d as compared to unsubstituted terry-
lenediimide 3. Compound 20d has a light violet colour in so-
lution, as opposed to the blue colour of terrylenediimide 3.
In concentrated sulfuric acid, the colour of 20d changes to
748 cmÀ1
(15247mÀ1 cmÀ1); MS (FD, 8 kV): m/z (%): 357.2 (100) [M+]; elemental
;
UV/Vis (CHCl3): lmax (e)=359 (13244), 344 nm
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Terrylenediimide Fluorescent Dyes
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analysis calcd (%) for C12H18NO2Br: C 60.35, H 4.50, N 3.91; found: C
60.36, H 4.79, N 3.95.
stirred for 3 h at 1308C. After cooling to room temperature, the mixture
was poured into water (100 mL) to give a precipitate. The dark crude
product was washed with ethanol until the colour of the filtrate became
light red. A blue solid was obtained by recrystallisation from chloroform/
ethanol (3.5 g, 42%). The analytical data correspond to those in the liter-
ature.[7]
N-(2,6-Diisopropylphenyl)-9-(4-N-(2,6-diisopropylphenyl)naphthalene-
1,8-dicarboximide)perylene-3,4-dicarboximide (10a): Compounds
8
(5.0 g, 8.2 mmol) and 9a (7.2 g, 16.5 mmol) were dissolved in toluene
(380 mL). A solution of Na2CO3 in water (20 mL, 1m) and ethanol
(13 mL) were added, and the mixture was flushed with argon. [Pd(PPh3)4]
catalyst (400 mg, 0.3 mmol) was added, and the reaction mixture stirred
under argon for 16 h at 808C. The reaction mixture was cooled to room
temperature. The organic phase was separated, and the solvent evaporat-
ed under reduced pressure. The crude material was purified by column
chromatography on silica (CH2Cl2) to give 10a (6.19 g, 90%). The analyt-
ical data corresponded to those in the literature.[7]
N-(2,6-Diisopropylphenyl)-9-(4-bromo-2,6-diisopropylphenylnaphtha-
lene-1,8-dicarboximide)perylene-3,4-dicarboximide (13): Compounds
8
(3.0 g, 4.9 mmol) and 11 (3.42 g, 12.0 mmol) were dissolved in toluene
(315 mL). A solution of Na2CO3 (13.22 g, 0.124 mol) in water (63 mL)
and ethanol (20 mL) was added, and the mixture flushed with argon.
[Pd(PPh3)4] catalyst (300 mg, 0.25 mmol) was added, and the reaction
mixture stirred under argon for 16 h at 908C. The reaction mixture was
cooled to room temperature. The resulting salt was collected by filtration.
The salt was poured into concentrated HCl (200 mL). The resulting 12
was collected by filtration and used without further purification in the
next step (2.69 g, 80%). Compound 12 (1.6 g, 2.36 mmol), 4-bromo-2,6-
diisopropylaniline (7.0 g, 27.3 mmol) and propionic acid (40 mL) were
added to a 250 mL flask. The reaction mixture was stirred for 16 h at
1508C. Water (150 mL) was poured into the cooled solution to obtain a
red precipitate, which was collected by filtration. The product was puri-
fied by column chromathography (CH2Cl2) to give 13 (0.84 g, 38%).
M.p. >3808C; 1H NMR (700 MHz, C2D2Cl4, 1208C): d=8.75 (d, J=
7.1 Hz, 1H), 8.66 (m, 3H), 8.59 (d, J= Hz,7.4, 1H), 8.56 (d, J=7.7 Hz,
1H), 8.5 (d, J=7.2 Hz, 2H), 7.92 (d, J=8.2 Hz, 1H), 7.88 (d, J=7.2 Hz,
1H), 7.69 (d, J=7.4 Hz, 1H), (t, J=7.4 Hz, 1H), 7.51 (m, 2H), 7.42 (m,
3H), 7.29 (m, 2H), 2.87 (m, 2H),1.16 ppm (m, 24H),; 13C NMR (75 MHz,
C2D2Cl2, 258C): d=164.4, 164.3, 148.9, 146.5, 145.3, 139.5, 137.7, 137.4,
133.8, 133.5, 132.2, 131.9, 131.8, 131.6, 130.9, 130.3, 130.0, 129.7, 129.5,
129.5, 129.3, 128.6, 127.8, 127.7, 127.3, 124.6, 124.4, 124.0, 123.7, 123.2,
122.9, 121.8, 121.7, 121.2, 121.1, 29.6, 29.4, 24.1, 23.9 ppm; IR (KBr
pellet) n˜ =2961, 1704, 1665, 1589, 1354, 1237, 846 cmÀ1; UV/Vis (CHCl3):
lmax (e)=513 (40106), 487 (39233), 355 (14316), 340 (16291), 264 nm
(28265mÀ1 cmÀ1); MS (FD, 8 kV): m/z (%): 915.9 (100) [M+]; elemental
analysis calcd (%) for C58H47BrN2O4: C 76.06, H 5.17, N 3.06; found C
76.07, H 5.05, N 2.99.
N-(2,6-Diisopropylphenyl)-9-(4-N-cyclohexylnaphthalene-1,8-dicarbox-
imide)perylene-3,4-dicarboximide (10b):
8 (1.9 g, 3.1 mmol) and 9b
(0.74 g, 2.0 mmol) were dissolved in toluene (200 mL). A solution of
K2CO3 in water (40 mL, 1m) was added, and the mixture flushed with
argon. [Pd(PPh3)4] catalyst (300 mg, 0.25 mmol) was added, and the reac-
tion mixture stirred under argon for 16 h at 808C. The reaction mixture
was cooled to room temperature. The organic phase was separated, and
the solvent evaporated under reduced pressure. The crude material was
purified by column chromatography on silica (CH2Cl2) to give 10b (2.1 g,
90%). M.p. >2868C; 1H NMR (500 MHz, C2D2Cl4, 258C): d=8.67 (d,
J=7.4 Hz, 1H), 8.63 (m, 2H), 8.53 (d, J=8.3 Hz, 1H), 8.48 (m, 2H), 7.81
(m, 2H), 7.64 (d, J=7.7 Hz, 1H), 7.59 (m, 1H), 7.48 (t, J=7.6 Hz, 1H),
7.42 (m, 2H), 7.28 (d, J=7.8 Hz, 2H), 2.71 (d, J=6.8 Hz, 2H), 2.56 (m,
2H), 1.89 (m, 2H), 1.74 (m, 4H), 1,44 (m, 2H), 1.14 ppm (d, J=6.8 Hz,
12H); 13C NMR (125 MHz, C2D2Cl4, 258C): d=163.6, 163.4, 163.0, 144.8,
143.9, 138.6, 138.2, 136.6, 136.3, 134.3, 132.5, 130.4, 130.3, 129.6, 129.1,
128.8, 128.0, 127.4, 126.1, 123.3, 122.2, 122.0, 120.6, 120.4, 28.3, 23.3 ppm;
IR (KBr pellet) n˜ =2958, 2930, 2860, 1701, 1662, 1590, 1576, 1465, 1357,
1235, 1180, 813, 783, 754 cmÀ1; UV/Vis (CHCl3): lmax (e)=264 (25703),
336 (12882), 484 (35481), 512 nm (36307mÀ1 cmÀ1); MS (FD, 8 kV): m/z
(%): 757.8 (100) [M+]; elemental analysis calcd (%) for C52H42NO4: C
82.3, H 5.58, N 3.69; found C 82.45, H 5.67, N 3.70.
N-(2,6-Diisopropylphenyl)-N’-cyclohexylterrylene-3,4:11,12-tetracarbox-
diimide (3b): Compound 10b (700 mg, 0.9 mmol), K2CO3 (220 mg,
1.6 mmol) and ethanolamine (10 mL) were stirred under argon for 12 h
at 808C. After cooling to room temperature, the solution was poured
into ethanol (20 mL). The precipitate was collected by filtration, washed
with water, dried under vacuum, and purified by column chromatography
on silica gel (CH2Cl2) to yield the blue product 3b (660 mg, 95%). M.p.
>3008C; 1H NMR (500 MHz, C2D2Cl4, 1008C): d=8.54 (d, J=8.5 Hz,
2H), 8.21 (m, 5H), 8.13 (d, J=8.5 Hz, 2H), 7.43 (t, 1H), 7.29 (d, J=
7.9 Hz, 2H), 5.05 (m, 1H), 2.74 (m, 2H), 2.47 (m, 2H), 1.85 (m, 2H), 1.7
(m, 4H), 1.38 (m, 2H), 1.14 ppm (m, 12H); 13C NMR (125 MHz,
C2D2Cl4, 1008C): d=163.81, 163.65, 163.1, 144.8, 143.1, 138.5, 136.7,
136.4, 132.5, 131.3, 130.4, 130.1, 129.7, 129.0, 128.8, 128.4, 127.7, 127.4,
126.8, 126.1, 123.4, 122.7, 122.5, 120.5, 120.4, 28.4, 25.9, 24.8, 23.3 ppm;
IR (KBr pellet) n˜ =2961, 2929, 2867, 1995, 1653, 1585, 1379, 1357, 1328,
1247, 1183, 1112, 842, 810, 751 cmÀ1; UV/Vis (CHCl3): lmax (e)=600
(43325), 652 nm (81850mÀ1 cmÀ1); MS (FD, 8 kV): m/z (%): 756 (100)
[M+]; elemental analysis calcd (%) for C52H40NO4: C 81.3, H 5.58, N
3.69; found C 81.19, H 5.72, N 3.56.
N-(4-Bromo-2,6-diisopropylphenyl)-N’-(2,6-diisopropylphenyl)terrylene-
3,4:11,12-tetracarboxdiimide (14): Compound 13 (350 mg, 0.38 mmol),
K2CO3 (2.5 g, 18 mmol) and ethanolamine (3.5 mL) were stirred under
argon for 3 h at 1608C. After cooling to room temperature, the solution
was poured into water (200 mL). The precipitate was collected by filtra-
tion, washed with water, dried under vacuum and purified by column
chromatography on silica gel (CH2Cl2) to yield the blue product 14
1
(314 mg, 90%). M.p. >4008C; H NMR (300 MHz, C2D2Cl4, 1208C): d=
8.69 (m, 8H), 8.60 (d, J=7.9 Hz, 4H), 7.42 (t, J=7.6 Hz, 1H), 7.40 (s,
1H), 7.28 (d, J=7.7 Hz, 2H), 2.73 (m, 4H), 1.17 (d, J=2.7 Hz, 12H),
1.15 ppm (d, J=2.7 Hz, 12H); 13C NMR (75 MHz, C2D2Cl4, 1208C): d=
163.7, 163.6, 148.8, 136.5, 136.2, 132.0, 132.0, 131.4, 130.6, 129.4, 129.1,
127.6, 124.8, 124.7, 124.0, 122.7, 122.3, 121.9, 121.8, 29.6, 29.4, 24.0,
23.7 ppm; IR (KBr pellet) n˜ =2963, 2930, 2870, 1704, 1663, 1585, 1378,
1359, 1332, 1250, 1180, 850, 810, 752 cmÀ1; UV/Vis (CHCl3): lmax (e)=655
(129700), 602 (67247), 557 nm (21792mÀ1 cmÀ1); MS (FD, 8 kV): m/z
(%): 914.1 (100) [M+]; elemental analysis calcd (%) for C58H45BrN2O4:
C 76.23, H 4.96, N 3.07; found C 76.08, H 4.89, N 3.22.
N,N’-Di(2,6-diisopropylphenyl)terrylene-3,4:11,12-tetracarboxdiimides
(3): Multistep synthesis of terrylenetetracarboxdiimides (Scheme 2):
Compound 10a (7.0 g, 8.37 mmol), K2CO3 (1.0 g, 7.17 mmol) and etha-
nolamine (1.07 g, 23.9 mmol) were stirred under argon for 12 h at 808C.
After cooling to room temperature, the solution was poured into metha-
nol (20 mL). The precipitate was collected by filtration, washed with
water, dried under vacuum and purified by column chromatography on
silica gel (CH2Cl2) to yield the blue product 3 (6.9 g, 95%). The analyti-
cal data corresponded to those in the literature.[7]
N-(5-Carboxpentyl)naphthalene-1,8-dicarboxiimide (17a): 1,8-Naphtha-
lene anhydride (4.0 g, 20.2 mmol), 6-aminocaproic acid (5.1 g, 40 mmol)
and propionic acid (250 mL) were added to a 500 mL flask. The reaction
mixture was stirred for 15 h at 1408C. The cooled solution was added to
water (1.0 L) to give a white precipitate. The solid was obtained by filtra-
tion. The product 17a was purified by recrystallisation (dichloromethane
and ethanol; 5.2 g, 85%). M.p. 1368C; 1H NMR (250 MHz, CD2Cl2,
258C): d=8.53 (d, J=7.5 Hz, 2H), 8.20 (d, J=7.5 Hz, 2H), 7.73 (t, J=
7.5 Hz, 2H), 4.13 (m, 2H), 2.37 (m, 2H), 1.72 (m, 4H), 1.47 ppm (m,
2H); 13C NMR (62.5 MHz, CD2Cl2, 258C): d=179.7, 164.3, 134.1, 131.9,
131.2, 128.3, 127.2, 123.0, 40.3, 34.1, 27.9, 26.8, 24.7 ppm; IR (KBr pellet)
n˜ =3446, 2940, 2862, 2361, 1698, 1661, 1625, 1590, 1457, 1438, 1386, 1344,
One-pot synthesis of terrylenetetracarboxdiimide (Scheme 3): Perylene-
dicarboximide 15 (4.8 g, 10 mmol), naphthalenedicarboximide 16 (14.2 g,
40 mmol) and tBuONa (19.2 g, 0.2 mol) were added to a 100 mL Schlenk
flask. 1,5-Diazabicyclo[4.3.0]non-5-ene (DBN; 30 mL) and diglyme
(25 mL) were then injected into the flask under argon. The mixture was
1312, 1260, 1235, 1167, 1139, 1104, 1068, 939, 846, 781, 738, 648, 542 cmÀ1
UV/Vis (CHCl3): lmax (e)=334 (14669), 349 nm (13294mÀ1 cmÀ1); MS
;
Chem. Eur. J. 2005, 11, 3959 – 3967
www.chemeurj.org
ꢁ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3965

K. Mꢀllen et al.
(FD, 8 kV): m/z (%): 311.3 (100) [M+]; elemental analysis calcd (%) for
C18H17NO4: C 69.44, H 5.50, N 4.50; found C 69.44, H 5.51, N 4.51.
washed with water (100 mL) three times. The crude product was purified
by column chromatography on silica with chloroform to give a violet
solid (34 mg, 34%). M.p. >3008C; 1H NMR (250 MHz, CD2Cl2, 258C):
d=9.88 (s, 4H), 8.42 (s, 4H), 7.51 (t, J=7.5 Hz, 2H), 7.35 (t, J=7.5 Hz,
2H), 3.49 (m, 8H), 2.84 (m, 8H), 2,74 (m, 4H), 1.83 (m, 20H), 1.37 (m,
4H), 1.15 ppm (d, J=7.0 Hz, 24H); 13C NMR (75 MHz, CD2Cl2, 258C):
d=164.6, 151.5, 146.5, 132.2, 132.0, 131.3, 131.0, 129.5, 126.4, 125.2, 124.3,
122.8, 122.6, 120.9, 29.4, 26.2, 24.3, 24.0 ppm; IR (KBr pellet) n˜ =2925,
2853, 2361, 2335, 1696, 1658, 1583, 1452, 1413, 1328, 1259, 1203, 1094,
1025, 859, 806, 672, 552 cmÀ1; UV/Vis (CHCl3): lmax (e)=538 (4099),
804 nm (21582mÀ1 cmÀ1); MS (FD, 8 kV): m/z (%): 1167.5 (100) [M+]; el-
emental analysis calcd (%) for C78H82N6O4: C 80.24, H 7.08, N 7.20;
found C 80.11, H 7.18, N 7.01.
N-(2,6-Diisopropylphenyl)-N’-(5-carboxpentyl)terrylene-3,4:11,12-tetra-
carboxydiimide (18a): Compound 15 (960 mg, 2.0 mmol), naphthalenedi-
carboximide derivative 17a (1.25 g, 4.0 mmol) and tBuONa (3.84 g,
40 mmol) were added to
a 100 mL Schlenk flask. 1,5-Diazabicyclo-
[4.3.0]non-5-ene (4.0 mL) and diglyme (4.0 mL) were then injected into
the flask under argon. The mixture was stirred for 2 h at 1308C. After
cooling to room temperature, the mixture was poured into water
(100 mL) to give a precipitate. The dark crude product was washed with
chloroform until the colour of the filtrate became light red, and then
with methanol (100 mL) three times to give a violet-blue solid (potassium
salt). This solid was dissolved in methanol. When aqueous HCl solution
was added, a blue solid was obtained. The product 18a was purified by
recrystallisation from chloroform/ethanol (560 mg, 36%). M.p. >3008C;
1H NMR (300 MHz, C2D2Cl4, 1208C): d=8.67 (d, J=7.8. Hz, 2H), 8.55
(m, 8H), 8.45 (d, J=7.8 Hz, 2H), 7.42 (t, J=7.5 Hz, 1H), 7.28 (d, J=
7.5 Hz, 2H), 4.18 (m, 2H), 2.75 (m, 2H), 2.37 (m, 2H), 1,76 (m, 2H),
1.51 (m, 2H), 1.17 ppm (d, J=6.9 Hz, 2H); 13C NMR (175 MHz,
C2D2Cl4, 1408C): d=179.2, 163.8, 146.5, 132.0, 131.6, 129.4, 124.7, 124.1,
122.9, 122.7, 121.9, 121.8, 40.6, 34.4, 29.6, 28.2, 26.9, 24.7, 24.0 ppm; IR
(KBr pellet) n˜ =3432, 2958, 2362, 2336, 1694, 1653, 1583, 1431, 1356,
1303, 1248, 1202, 1023, 841, 808, 749, 673, 520 cmÀ1; UV/Vis (CHCl3):
lmax =556, 600, 653 nm (the extinction coefficients could not be measured
due to low solubility); MALDI-TOF MS: m/z (%): 788.0 (100) [M+]; el-
emental analysis calcd (%) for C52H40N2O6: C 79.17, H 5.11, N 3.55;
found C 78.91, H 5.02, N 3.79.
1,6,9,14-Tetra(4-sulfonylphenoxy)-N,N’-(2,6-diisopropylphenyl)terrylene-
3,4:11,12-tetracarboxidiimide (21): Compound 20c (120 mg, 1.0 mmol)
was added to concentrated sulfuric acid (1.0 mL). The flask was sealed,
and the mixture stirred for 15 h at room temperature. Water (3.0 mL)
was slowly added to the flask to form a precipitate, which was collected
by filtration. The solid was washed with dichloromethane (50 mL) three
times and then dried at 758C under vacuum to give blue-green 20c
(140 mg, 94%). M.p. >3008C; 1H NMR (250 MHz, CD3OD, 258C): d=
8.76 (s, 4H), 7.75 (s, 4H), 7.54 (d, J=8.0 Hz, 8H), 7.04 (t, J=7.5 Hz,
2H), 6.93 (d, J=7.5 Hz, 4H), 6.79 (d, J=8.0 Hz, 8H), 2.34 (m, 4H),
0.7 ppm (d, J=7.5 Hz, 24H); 13C NMR (62.5 MHz, CD3OD, 258C): d=
164.2, 158.5, 155.1, 147.1, 132.1, 131.6, 130.5, 129.9, 129.8, 129.6, 129.5,
127.9, 125.4, 125.0, 124.8, 123.5, 119.5, 30.3, 24.4 ppm; IR (KBr pellet)
n˜ =3424, 2361, 1700, 1647, 1589, 1490, 1328, 1280, 1178, 1126, 1067, 1031,
1006, 878, 849, 651, 578 cmÀ1; UV/Vis (water): lmax (e)=437 (4020), 640
(23898) 685 nm (17875mÀ1 cmÀ1); MALDI-TOF MS: m/z (%): 1524.0
(100) [M+]; elemental analysis calcd (%) for C82H62N2O8S4: C 64.64, H
4.10, N 1.84; found C 64.21, H 4.01, N 1.75.
N,N’-(2,6-Diisopropylphenyl)-1,6,9,13-tetra[4-(1,1,3,3-tetramethylbutyl)-
phenoxy]terrylene-3,4,11,12-tetracarboxidiimide (20a): Tetrabromoterry-
lenediimide 19 (300 mg, 0.279 mmol), tert-octylphenol (336 mg,
1.95 mmol) and K2CO3 (134 mg, 0.97 mmol) were heated in N-methylpyr-
rolidone (50 mL) at 808C under argon for 8 h. After cooling to room
temperature the reaction mixture was poured into HCl (2N, 100 mL).
The crude solid was separated under vacuum. Column chromatography
on silica gel with chloroform gave 20a (371 mg, 86%). M.p. >3008C;
1H NMR (500 MHz, CDCl3, 258C): d=9.48 (s, 4H), 8.15 (s, 4H), 7.35 (m,
10H), 7.19 (d, J=7.63 Hz, 4H), 7.07 (d, J=8.54 Hz, 8H), 2.57 (h, 4H),
1.52 (s, 8H), 1.02 (d, J=6.41 Hz, 24H), 0.64 ppm (s, 36H); 13C NMR
(62.5 MHz, CDCl3, 258C): d=162.21, 154.49, 152.12, 146.31, 144.68,
129.97, 128.16, 127.26, 124.78, 120.96, 118.40, 56.36, 37.57, 31.52, 30.57,
28.95, 28.26, 23.26 ppm; IR (KBr pellet) n˜ =2960, 2931, 2870, 1705, 1670,
1587, 1503, 1325, 1284, 1210, 1183, 1013, 844, 811 cmÀ1; UV/Vis (CHCl3):
lmax (e)=679 (99716), 623 nm (50721mÀ1 cmÀ1); MS (FD, 8 kV): m/z (%):
1651.9 (100) [M+]; elemental analysis calcd (%) for C114H126N2O8: C
82.87, H 7.69, N 1.70; found C 82.84, H 7.69, N 1.69.
Acknowledgements
Financial support from the German Science Foundation (SFB), Bio-Or-
ganics Nanostructuring for molecular electronics (BIONICS) and BASF
AG are gratefully acknowledged.
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1,6,9,14-Tetraphenoxy-N,N’-(2,6-diisopropylphenyl)terrylene-3,4,11,12-tet-
racarboxidiimide (20c): Compound 19 (230 mg, 0.2 mmol), phenol
(200 mg, 2.13 mmol) and K2CO3 (138 mg, 1.0 mmol) were heated in N-
methylpyrrolidone (30 mL) at 808C under argon for 15 h. After cooling
to room temperature, the reaction mixture was poured into HCl (2n,
100 mL). The crude solid was separated under vacuum. Column chroma-
tography on silica gel with chloroform gave 20c (216 mg, 90%). M.p.
>3008C; 1H NMR (250 MHz, C2D2Cl2, 258C): d=9.50 (s, 4H), 8.25 (s,
4H), 7.44 (m, 10H), 7.31 (d, J=7.5 Hz, 4H), 7.20 (m, 12H), 2.69 (m,
4H), 1.10 ppm (d, J=6.75 Hz, 4H); 13C NMR (62.5 MHz, C2D2Cl2,
258C): d=163.3, 156.0, 154.6, 146.2, 131.4, 131.2, 130.6, 129.6 , 129.2,
129.1, 126.6, 124.7, 124.2, 124.1, 123.3, 122.4, 119.3, 29.2, 23.9 ppm; IR
(KBr pellet) n˜ =2961, 2925, 2868, 2362, 2337, 1706, 1668, 1587, 1448,
1412, 1349, 1326, 1275, 1198, 1053, 1014, 869, 808, 748, 687, 581, 526 cmÀ1
;
UV/Vis (CHCl3): lmax (e)=429 (11706), 618 (70504), 671 nm
(135333mÀ1 cmÀ1); MS (FD, 8 kV): m/z (%): 1203.5 (100) [M+]; elemen-
tal analysis calcd (%) for C82H62N2O4: C 81.84, H 5.19, N 2.33; found C
81.76, H 5.12, N 2.11.
N,N’-(2,6-Diisopropylphenyl)-1,6,9,13-tetra(N-piperidyl)-terrylene-
3,4:11,12-tetracarboxidiimide (20d): Compound 19 (100 mg, 0.09 mmol)
and piperidine (2.0 mL) were added to a 25-mL Schlenk flask under
argon. The solution was stirred for five days at 858C. The cooled reaction
mixture was poured into water (30 mL). The resulting precipitate was
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Received: November 19, 2004
Published online: April 21, 2005
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3967