Quaterrylenebis(dicarboximide)s: Near infrared absorbing and emitting dyes

Article abstract of DOI:10.1039/a804337j

New ladder-type chromophores, the quaterrylenebis(dicarboxdiimide)s 2, 18 and 23, have been synthesised which, despite their extended π-system, exhibit good solubility in organic solvents and film forming properties when adequately substituted. These unpr

Full text of DOI:10.1039/a804337j

J O U R N A L O F
Quaterrylenebis(dicarboximide)s: near infrared absorbing and
emitting dyes
Yves Geerts,a† Heribert Quante,a Harald Platz,a Rainer Mahrt,b M. Hopmeier,b Arno Bo¨hmc and
Klaus Mullen*a‡
¨
C H E M I S T R Y
aMax-Planck-Institut fur Polymerforschung, Ackermannweg 10, D-55128 Mainz, Germany
¨
bFachbereich Physikalische Chemie und Zentrum fur Materialwissenschaffen, Philipps Universitat,
¨
¨
Renthof 5, D35032 Marburg, Germany
cBASF AG, ZDP/0-M311, 67056 Ludwigshafen, Germany
Received 8th June 1998, Accepted 2nd September 1998
New ladder-type chromophores, the quaterrylenebis(dicarboxdiimide)s 2, 18 and 23, have been synthesised which,
despite their extended p-system, exhibit good solubility in organic solvents and film forming properties when
adequately substituted. These unprecedented dyes, which absorb and even emit light in the NIR window, are also
characterized by oustanding chemical, thermal and photochemical stability with regard to their absorption range.
The potential formation of J-aggregates in strongly acidic media has been investigated and has been ruled out by
combined 1H NMR and UV–VIS–NIR spectroscopy experiments. In addition, their photophysical and
electrochemical characteristics have been explored and are discussed.
a
Introduction
b
The search for novel, near infrared (NIR) absorbing and
emitting dyes is a challenge in dyestuff chemistry, mainly
c
d
because of the potential high-technology applications in optical
O
N
O
O
N
O
recording, thermally written displays, laser printers, laser fil-
ters, infrared photography and medicine.1 Despite the high
demand, only a few NIR dyes, such as cyanine dyes, are
effectively used in practice. A prerequisite in the design of
chromophores is the consideration of their chemical, thermal
and photochemical stability.2 Perylene derivatives and, in
particular, perylenebis(dicarboximide)s 1, are well-known for
their outstanding chemical, thermal and photochemical inert-
ness.3,4 Their uses range from paints and varnishes to high-
technology applications such as tracers in fluorescence analyt-
ical assays,5 charge-transport in Langmuir–Blodgett films,6
photovoltaic cells,7 xerography,8 optical switches,9 laser-dyes10
and fluorescent collectors.11 Clearly, new chromophores such
as quaterrylenebis(dicarboximide)s 2, which combine the out-
standing properties of perylenebis(dicarboximide)s 1 with NIR
absorption, are highly desirable.
2
1
5
6
Ar
Ar
Ar
O
O
O
O
12
11
7
8
Ar
O
N
O
O
N
O
1a
1b
The first attempts at extending the p-system of perylene 3
to higher rylenes, namely terrylene 4 and quaterrylene 5, were
carried out by Clar.12 However, due to the lack of adequate
alkyl substitution, resulting in extreme insolubility, the purifi-
cation and characterization of terrylene 4 and quaterrylene 5
were not possible.13
More recently, we synthesized the first soluble oligorylene
series 6.14 The introduction of tert-butyl groups at the periph-
ery of the rigid aromatic structure drastically improved their
solubility in common organic solvents. Remarkably enough,
terrylene, quaterrylene and even pentarylene were fully charac-
terized and their photophysical behavior correlated with their
structure.14b
the perylenebisamidine 9.16 These NIR dyes are characterized
by high photochemical and thermal stability. Moreover terry-
leneimides 7 and 8 exhibit oustanding quantum fluorescence
yields of 0.9 0.1 and 0.6 0.1, respectively.
In this paper, we report the detailed synthesis and the
characterization of quaterrylenebis(dicarboximide)s 2, 18 and
23, which are higher homologues of perylenebis(dicarboxim-
ide)s 117 and of terrylenebis(dicarboximide)s 7.15 In addition,
the photophysical, thermal and electrochemical properties of
quaterrylenebis(dicarboximide)s 2, 18 and 23 are compared to
those of perylenebis(dicarboximide)s 1 and to terrylenebis-
(dicarboximide)s 7 and discussed in the light of their structures.
We have also reported some new fluorescent dyes emitting
at long wavelengths (600<l<750 nm) and even in the NIR
range (l>750 nm), which are structurally related to quaterry-
lenebis(dicarboximide)s, namely the terryleneimides 7,815 and
Results and discussion
Synthesis
The synthetic pathway to quaterrylenebis(dicarboximide)s 2a,b
is illustrated in Scheme 1. The key building block for the synthesis
of quaterrylenebis(dicarboximide)s is the N-substituted pery-
lene-3,4-dicarboximides 11a,b which are obtained via the partial
†Chercheur Qualifie´ au Fonds National de le Recherche Scientifique,
Universite´ libre de Bruxelles, Chimie Macromole´culaire, CP 206/1,
Boulevard du Triomphe, 1050 Bruxelles, Belgium.
‡E-mail: muellen@mpip-mainz.mpg.de
J. Mater. Chem., 1998, 8(11), 2357–2369
2357

R
N
O
O
O
N
O
O
N
O
2
1
5
6
20
19
7
8
R
R
R
R
18
17
9
10
16
15
11
12
O
O
N
O
O
N
R
O
R'
8a,b
7a,b
2a R = C12H25
b R = C6H3-2,6-Pri2
c R = Bu
Br
Br
Br
Br
O
N
N
O
N
N
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
O
O
O
O
O
O
O
O
N
N
O
O
N
N
Br
Br
Br
Br
4
3
5
9-syn
a R = H, b R = OAr
9-anti
R' = C8H17, C6H3-2,6-Pri2
However, we recently reported some developments in the
field of organometallic aryl–aryl coupling which allows the
synthesis of 14a,b in higher yields.15,17 Specifically, two
organometallic synthetic pathways from the monobromo N-
substituted perylene-3,4-dicarboximide 12a,b to the biperylene
14a,b have been attempted. The first synthetic route, a one
step Yamamoto homocoupling20 with the zero-valent nickel
n
catalyst bis(cycloocta-1,5-diene)nickel(0) [Ni(cod) ] has suc-
2
6
a
b
c
d
cessfully been applied and afforded the biperylenes 14a,b
in excellent yields (83–89%). The second synthetic route to
the biperylene 14b is based on the Stille heterocoupling of
monobromo N-substituted perylene-3,4-dicarboximide 12b
with its stannylated analogue 13b in the presence of the
zero-valent tetrakis(triphenylphosphine)palladium catalyst
n
0
1
2
3
decarboxylation of perylenedicarboxylic anhydrides 10a,b.18,19
The bromination of the N-substituted perylene-3,4-dicarboxim-
ides 11a,b at position 9 leads to the monobromo N-substituted
perylene-3,4-dicarboximides 12a,b in 94–98% yield. Misono
and Nagao have synthesized the biperylene 14c via an Ullmann
coupling of the 9-bromo-N-butylperylene-3,4-dicarboximide
12c in low yield.18,19 The low yield has been attributed to the
large amount of side products rendering the purification diffi-
cult and to the inadequate alkyl substitution at the imide
position resulting in low solubility of the biperylene 14c.
[Pd(PPh ) ].15,21 This route requires an additional step, but
3 4
presents the advantage of replacing the relatively toxic, air-
sensitive and expensive Ni(cod) by the more conventional
2
Pd(PPh ) . Moreover, the coupling of two differently substi-
3 4
tuted perylene derivatives, resulting in non-symmetrically N-
substituted quaterrylenebis(dicarboximide)s, is therefore pos-
sible. This significantly widens the scope of applications of the
quaterrylenebis(dicarboximide)s which could be introduced as
side chain functions in polymers to combine the processability
2358
J. Mater. Chem., 1998, 8(11), 2357–2369

R
N
R
N
R
N
O
O
O
O
O
O
O
O
O
O
Br
O
O
O
10a–c
11a–c
12a–c
R
N
R
N
O
O
R
N
O
O
SnBu3
13b
O
N
R
O
N
R
a R = C12H25
b R = C6H3-2,6-Pri2
c R = Bu
2a,b
14a–c
Scheme 1 Synthetic pathway to quaterrylenebis(dicarboximide) 2a.
and good film-forming properties of polymers with the intrinsic
properties of quaterrylenebis(dicarboximide)s. One could also
selectively introduce another functional group, e.g. an electron
donor for photoinduced electron transfer or a biologically
active molecule for NIR fluorescence analytical assays.5
The last synthetic step of Scheme 1 involves the cyclization
of the biperylenes 14a,b into quaterrylenebis(dicarboximide)s
2a,b in the presence of a base and an oxidizing agent.23,24
Specifically, the cyclization reaction has been carried out in a
KOH/ethanol melt containing glucose as oxidizing agent at
120 °C.24 The resulting quaterrylenebis(dicarboximide) 2b was
readily purified by recrystallization, affording the desired prod-
uct 2b in 83% yield, whereas the less soluble quaterrylenebis-
(dicarboximide) 2a was obtained in lower yield (37%) and was
purified by extraction of the by-products with chloroform. In
the case of quaterrylenebis(dicarboximide) 2b, further purifi-
cation by column chromatography was only performed for
the preparation of analytical samples.
The quaterrylenebis(dicarboximide) 2a is only slightly
soluble in organic solvents (typically <10−5 ) at room
temperature and is better viewed as a pigment than a dye.
However for numerous applications, good processability, i.e.
high solubility in organic media and good film-forming proper-
ties, is required. As previously mentioned, one way to achieve
processability is to introduce quaterrylenebis(dicarboximide)
2a as a pendant group on a polymer chain. Another method,
which consists of introducing phenoxy substituents into the
bay-regions of the aromatic core, is well-known in the case of
the perylenebis(dicarboximide) 1b.15,16,25 The introduction of
substituents in the bay-region of the perylenebis(dicarboxim-
ide) 1b presents the additional advantage of further extending
the absorption maxima to longer wavelength. In analogy to
perylenebis(dicarboximide) 1b, we have attempted the syn-
thesis of tetraphenoxy substituted quaterrylenebis(dicarboxim-
ide) 18. The synthetic pathway to the tetraphenoxy substituted
quaterrylenebis(dicarboximide) 18 is given in Scheme 2 and
shares many similarities with that of the unsubstituted quater-
rylenebis(dicarboximide)s 2a,b.
The three-fold bromination of 11 under drastic conditions
gives the perylene tribromide 15 in excellent yield (91%). The
selective nucleophilic substitution under basic conditions of
the two bromine atoms in the bay-regions with phenol deriva-
tives affords 16 in a yield of 33%. The moderate yield is due
to side reactions, namely the substitution of all three bromine
atoms by phenoxy groups and dehalogenation.
Comparable to the synthesis of the biperylenes 14a,b, the
Yamamoto coupling affords the biperylene 17 in a yield of
88%. The cyclization of 17 to the tetraphenoxy substituted
quaterrylenebis(dicarboximide) 18, in a yield of 85%, has been
carried out as described for the unsubstituted perylene 14. As
expected, the solubility of quaterrylenebis(dicarboximide) 18
is much higher than that of 2 and reaches ~10−2  in
J. Mater. Chem., 1998, 8(11), 2357–2369
2359

R
N
R
N
R
N
O
O
O
O
O
O
Br
Br
R'
R'
Br
Br
15
11
16
R
R
N
O
N
O
O
O
R'
R'
R'
R'
R = C6H3-2,6-Pri2
R' = OC6H4-4-But
R'
R'
R'
R'
O
N
R
O
O
N
R
O
18
17
Scheme 2 Synthetic pathway to quaterrylenebis(dicarboximide) 18.
chlorinated solvents. These encouraging results suggest that
an additional increase of solubility should result from an eight-
fold substitution by phenoxy groups of the quaterrylenebis-
(dicarboximide) core. Therefore, we have embarked on the
synthesis of octaphenoxy substituted quaterrylenebis(dicar-
boximide) 23 (Scheme 3).
and Oda28 where the catalyst, tetrakis(triphenylphosphine)-
nickel(0), is generated in situ.29 The biperylene 22 was then
obtained in 79% yield.
The reaction conditions used for the cyclization of biperyl-
enes 14 and 17 resulted, in the case of 22, also in the partial
cleavage of the phenoxy groups of the resulting octasubstituted
quaterrylenebis(dicarboximide) 23. Consequently, milder reac-
tion conditions have been applied to afford the octaphenoxy
substituted quaterrylenebis(dicarboximide) 24 in very low yield
(0.3%). The separation of octaphenoxy substituted quaterry-
lenebis(dicarboximide) 24 from numerous side products was
conducted by gel permeation chromatography (GPC) on
polystyrene as stationary phase with chloroform as eluent.
The entry point to the synthetic scheme is the perylenedicar-
boximide 20 carrying four phenoxy substituents, which has
been synthesized by hydrolysis of one imide function of
perylenebis(dicarboximide) 19 under basic conditions, fol-
lowed by decarboxylation with copper() oxide under vacuum.
Purification by chromatography and recrystallisation affords
tetraphenoxyperylenedicarboximide 20 in 53% yield. The
monobromination of 20 under the mild conditions described
by Mitchell26 with N-bromosuccinimide in dimethylformamide
leads selectively to bromoperylenedicarboximide 21 in high
yield (98%). Surprisingly enough, the Yamamoto coupling of
the bromoperylenedicarboximide 21 under the conditions pre-
viously described for the bromoperylenedicarboximides 13 and
16 resulted mainly in the cleavage of the phenoxy substituents.
The reason for this unexpected side reaction remains enigmatic
and could not be explained by simple mechanistic consider-
ations. However, this forced us to use another coupling
reaction reported by Sontheimer27 and modified by Iyoda
Structure elucidation
The structures of quaterrylenebis(dicarboximide)s were proven
by 1H and 13C NMR spectroscopy, field desorption mass spec-
troscopy (FD-MS), FT-IR spectroscopy and UV–VIS spec-
troscopy. Due to a plane of symmetry, the 1H NMR spectra of
quaterrylenebis(dicarboximide)s 2b, 18 and 23 have a simpler
appearance than those of their synthetic precursors, the bipery-
lene diimides 14, 17 and 22. The aromatic region of the 1H
NMR spectrum of quaterrylenebis(dicarboximide) 2b exhibits
2360
J. Mater. Chem., 1998, 8(11), 2357–2369

R
N
R
N
O
O
R
N
O
O
O
O
R'
R'
R'
R'
R'
R'
R'
R'
R'
R'
R'
R'
O
N
R
O
Br
19
20
21
R
R
N
O
N
O
O
O
R'
R'
R'
R'
R'
R'
R'
R'
R = Pr
R' = OC6H4-4-OC6H13
R'
R'
R'
R'
R'
R'
R'
R'
O
N
R
O
O
N
R
O
23
22
Scheme 3 Synthetic pathway to quaterrylenebis(dicarboximide) 23.
six resonances, as expected from the structure. The assignment,
based on 1H,1H correlated NMR analysis, of the resonnances
of 2b is given in Table 1. The chemical shifts for H-7,10,17,20
are almost identical to those of H-8,9,18,19 and no unambigu-
ous assignment of these protons has been achieved.
The 13C NMR spectrum of the tetraphenoxy substituted quat-
errylenebis(dicarboximide) 18 exhibits thirteen quaternary and
seven tertiary aromatic C-atoms, in accordance with the proposed
structure. However, a comprehensive assignment of the reson-
ances to the carbon atoms has been hindered by the lack of
appropriate reference compounds. The parent ions of the quater-
rylenebis(dicarboximide)s 2a,b, 18 and 23 are in good agreement
with the calculated masses and isotopic distributions corroborat-
ing, therefore, the proposed chemical structures. The FT-IR
spectra of the quaterrylenebis(dicarboximide)s 2a,b, 18 and 23
confirm the presence of the characteristic carbonyl bands, which
appear between 1700 and 1670 cm−1, depending on the substi-
tution at the nitrogen atoms.
The comparison of the UV–VIS–NIR spectra of perylenebis-
(dicarboximide) 1a and terrylenebis(dicarboximide) 7a with
the spectrum of quaterrylenebis(dicarboximide) 2b, given in
Fig. 1, is very instructive. Specifically, a bathochromic shift of
the absorption maxima from 526 nm for 1a, to 650 nm for 7a
and extending to 764 nm for 2b is clearly observed. The
extinction coefficient increases from e=80 000 −1 cm−1 for
the perylenebis(dicarboximide) 1a to e=120 000 −1 cm−1 for
terrylenebis(dicarboximide) 7a and up to e=162 000 −1 cm−1
for the quaterrylenebis(dicarboximide) 2b.
Table 1 1H NMR Chemical shifts of quaterrylene 2b (C D Cl ,
2
2 4
500 MHz, 135 °C)
d (ppm)
Type
H
Integration
4 H
8.68
d
2, 5, 12, 15
8.68, 8.63
d, d
7, 10, 17, 20,
8, 9, 18, 19
1, 6, 11, 16
a
b
c
8 H
4 H
2 H
4 H
4 H
24 H
A comparison with the absorption maximum of the previously
reported tetra-tert-butylquaterrylene 6c,14 shows that the two
dicarboximide functions at the peri-position of the quaterrylene-
bis(dicarboximide) 2b are responsible for a bathochromic shift of
more than 100 nm, as expected from the comparison of the
8.56
7.42
7.29
2.80
1.19
d
dd
d
q
d
d
J. Mater. Chem., 1998, 8(11), 2357–2369
2361

tion maxima of the quaterrylenebis(dicarboximide) 2b with
that of the tetraphenoxy substituted quaterrylenebis(dicarboxi-
mide) 18 and tetraphenoxy substituted perylenebis(dicarboxi-
mide)s 23 indicates a bathochromic shift of 19 (l =762 nm)
max
and 28 nm (l =790 nm), respectively. The observed
max
bathochromic shifts are due to the electron donating effect of
the phenoxy groups, and the effect has already been observed
in the case of tetraphenoxy substituted perylenebis(dicarboxi-
mide)s.16,17 Also of practical relevance, films of good optical
quality are easily cast from a solution of the tetraphenoxy
substituted quaterrylenebis(dicarboximide) 18. The VIS–NIR
spectra of 18, both in solution and as a film, show different
aspects. Instead of the sharp absorption maximum at 781 nm
accompanied by a shoulder at 709 nm observed in solution,
as a film 18 displays two absorption maxima of nearly equal
intensity at 724 and 795 nm. The high extinction coefficients
of quaterrylenebis(dicarboximide)s 2a,b, 18 and 23, which are
only equalled in the NIR range by a few squarylium dyes,1
suggest their use in optical data storage, where an excellent
signal to noise ratio could be reached.31
Fig. 1 UV–VIS–NIR spectra of perylenebis(dicarboximide) 1a (solid
line) terrylenebis(dicarboximide) 7a (dotted line) and quaterrylenebis-
(dicarboximide) 2b (solid bold line) in CH Cl .
2
2
UV–VIS spectrum of perylene 3 with the one of perylenebis(dicar-
boximide) 1a. The UV–VIS–NIR spectrum of quaterrylenebis-
(dicarboximide) 2b appears less structured than those of the
reference chromophores: the quaterrylene 6c, the perylenebis-
(dicarboximide) 1b, and the terylenebis(dicarboximide) 7a. We
attribute this feature to the enlarged p-system of quaterrylenebis-
(dicarboximide) 2b in regards to 1b and 7a.
J-Aggregates and absorption behavior in strongly acidic
media. A totally new situation arises when the quaterrylenebis-
(dicarboximide) 2b is dissolved in strongly acidic media.
Characteristically enough, a bathochromic shift of 112 nm is
obtained when 2b is dissolved in a mixture of sulfuric acid
and oleum (57%) (451) instead of chlorinated solvents.
Specifically, two peaks are observed, one at l=813 nm with
an e of 111 000 −1 cm−1, while the l of the second reaches a
value as high as 912 nm with an e of 581 000 −1 cm−1. The
This is due, we believe, to traces of water in the sulfuric
acid/oleum mixture, inducing differences in the oleum/
sulfuric ratio (see below). After dilution with water, the
quaterrylenebis(dicarboximide) 2b can be recovered, which
indicates that the chromophore is chemically stable even in
the presence of strong acids and oxidizing agents. The fact
that 2b remains chemically unaltered also indicates that the
large bathochromic shift and the sharp increase of e are
presumably due to the protonation of the carboximide func-
tions. The role of the protonation of this group on the NIR
spectrum of quaterrylenebis(dicarboximide) 2b was further
confirmed by slightly changing the nature of the acidic medium.
A dramatic change of the spectrum of 2b in concentrated
sulfuric acid, in comparison to chlorinated solvents, is also
observed. However, the NIR spectrum of quaterrylenebis-
(dicarboximide) 2b in concentrated sulfuric acid and in a
sulfuric acid/oleum mixture are not superimposable (Fig. 2).
Specifically, in concentrated sulfuric acid, three absorption
maxima are present at 868, 907 and 992 nm, with e of 137 000,
493 000 and 143 000 −1 cm−1, respectively, whereas only two
absorption maxima are observed in the sulfuric acid/oleum
mixture.
Properties
Solubility. The solubility of the quaterrylenebis(dicarboxim-
ide)s 2a,b, 18 and 23, which is the key to their processability,
has been investigated in chlorinated solvents at room and
elevated temperatures. The results are collected in Table 2.
The low solubility of quaterrylenebis(dicarboximide) 2a
compared to the much higher solubility of 2b is striking.
Despite the presence of two long dodecyl chains, quaterrylene-
bis(dicarboximide) 2a remains poorly soluble. The improved
solubility of quaterrylenebis(dicarboximide) 2b is due to faci-
ally encumbering substituents,31 i.e. the two 2,6-diisopro-
pylphenyl groups at the imide position, which decrease the
tendency of the quaterrylenebis(dicarboximide) core to form
p-stacks. The solubility of the quaterrylenebis(dicarboximide)
core is further increased by the introduction of four substitu-
ents in the bay-region, as shown by the good solubility of 18
at room temperature. Note as well that either the introduction
of eight substituents in the bay-regions or four substituents in
the bay-region and the additional effect of 2,6-diisopropylphe-
nyl groups give rise to similar solubilities.
value of l
is slightly higher than those reported earlier.17
max
Absorption behavior. From a practical aspect, it is worth
mentioning the almost colorless solutions, which are only
slightly blue, of quaterrylenebis(dicarboximide) 2b. This weak
absorption in the visible window strictly contrasts with the
deeply orange–red and blue colored solutions of perylene 1a
and terrylene 7a, respectively, observed for comparable concen-
trations. As hitherto mentioned, the substitution of the quater-
rylenebis(dicarboximide) in the bay-regions offers not only a
way to increase the solubility, but also to finely tune the
absorption maximum. For instance, comparison of the absorp-
Similarly, a large bathochromic shift and a dramatic increase
of e, by a factor 5.4, have also been observed for terrylenebis-
(dicarboximide) 7a in sulfuric acid as compared to a chloro-
form solution.15 Together, the large bathochromic shift and
the dramatic increase of e could suggest for both the quaterry-
lenebis(dicarboximide) 2b and terrylenebis(dicarboximide) 7a
the formation of a J-aggregate.32 J-Aggregates are supramol-
Table 2 Solubility and colors in solution of quaterrylenebis(dicarboximide)s
Solubility in
Solubility in
Color in
chlorinated solvents
Compound
CH Cl at r.t./mg ml−1
C H Cl at 135 °C/mg ml−1
2
2
2
2 4
2a
2b
15
20
—
—
~2
>80
>80
purple–green
green
green
<0.2
~30
~40
green
2362
J. Mater. Chem., 1998, 8(11), 2357–2369

strongly acidic solutions, i.e. tightly packed aggregates or
individual molecules, 1H NMR experiments in D SO were
2
4
conducted on the oligomeric series: perylenebis(dicarboximide)
1a, terrylenebis(dicarboximide) 7a and quaterrylenebis(dicar-
boximide) 2b. Since the three members of this oligomeric series
behave similarly, and for the sake of clarity, only the 1H NMR
spectra of the perylenebis(dicarboximide) 1a and the quaterry-
lenebis(dicarboximide) 2b are presented in Fig. 4.
Cl
Cl
Cl
Cl
N
N
N
N
Fig. 2 UV–VIS–NIR spectra of quaterrylenebis(dicarboximide) 2b in
a mixture of sulfuric acid and oleum (57%) (451) (solid line) and in
concentrated sulfuric acid (96%) (dotted line).
–
SO3Na
SO3
24
Three observations are made: Firstly, the 1H NMR spectra
of 1a, 7a and 2b are sufficiently resolved in a viscous solvent
such as D SO . Secondly, the 1H NMR spectra of 1a, 7a,
2
4
and 2b are independent of concentration in the range
10−2–10−3 . Thirdly, the chemical shifts of the protons of
1a, 7a, and 2b, located on the N-substituent and on the
aromatic core, are comparable within the oligomeric series. It
also follows from the 1H NMR spectra of 1a, 7a and 2b that
the protons adjacent to the isopropyl groups on the phenyl
substituents at the imide positions undergo rapid exchange
with deuterium in D SO . This has also been confirmed by
2
4
FD-MS analysis. Clearly, the well-resolved and concentration
independent spectra of 1a, 7a and 2b are inconsistent with the
formation of any aggregates in solution. Moreover, 1H NMR
spectra of a commercially available dye forming J-aggregates
Fig. 3 UV–VIS spectra of perylenebis(dicarboximide) 1a in CH Cl
2
2
(dotted line) and in concentrated sulfuric acid (96%) (solid line).
in D O, namely the benzimidocyanine 24, have been recorded
at 30 and 80 °C. Beside the characteristic peak of the solvent,
2
ecular assemblies of chromophores in which head-to-tail
arrangement of transition dipole moments results in a sharp,
intense and bathochromically shifted absorption band com-
pared to the isolated chromophore.32
the expected peaks of the dye were so broad that they could
not be detected, indicating the formation of tightly packed
aggregates. This last finding corroborates the view that no J-
aggregates are formed in the case of the oligomeric series 1a,
7a and 2b in concentrated sulfuric acid.
Therefore, the exact nature of the species present in
strongly acidic solutions of perylenebis(dicarboximide) 1a,
terrylenebis(dicarboximide) 7a and quaterrylenebis(dicarboxi-
mide) 2b remains unknown. One can only conclude that the
different behavior of 1a, 7a and 2b in chlorinated solvents
and strongly acidic media must be related to the protonation
After discussing the absorption spectra of terrylenebis(dicar-
boximide) 7a and quaterrylenebis(dicarboximide) 2b in
strongly acidic media, it is important to consider also that of
perylenebis(dicarboximide) 1a. Three observations are easily
made from the comparison between Fig. 2 and 3. Firstly, a
large bathochromic shift of all the visible spectrum occurs also
for perylenebis(dicarboximide) 1a in concentrated sulfuric acid
in comparison to chloroform solution. Secondly, the absorp-
tion peaks of 1a in concentrated sulfuric acid are not sharper
and are only slightly more intense than their corresponding
peaks in chloroform solution. The increase in intensity for the
absorption maxima of 1a in concentrated sulfuric acid in
comparison to chloroform solution, i.e. by a factor 1.4, is
significantly less pronounced than for terrylenebis(dicarboxim-
ide) 7a and quaterrylenebis(dicarboximide) 2b, i.e. by a factor
5.4 and 3.0, respectively. Thirdly, the shape of the absorption
curve of 1a in concentrated sulfuric acid remains somewhat
similar to the one in chloroform solution (Fig. 3). This obser-
vation contrasts with the very different shapes of the absorption
curves of the quaterrylenebis(dicarboximide) 2b in concen-
trated sulfuric acid and in chloroform solution. It should be
concluded for the perylenebis(dicarboximide) 1a that, despite
the large bathochromic shift observed, the absence of a sharp
and intense absorption in concentrated sulfuric acid seems not
to indicate the formation of J-aggregates.32
It is well documented that temperature and concentration
dependent 1H NMR experiments are particularly suited to the
investigation of the presence of aggregates in solution.33
Therefore, to elucidate the nature of the species present in
Fig. 4 1H NMR Spectra of (a) perylenebis(dicarboximide) 1a and (b)
quaterrylenebis(dicarboximide) 2b [D SO (96%), 500 MHz, 30 °C].
2
4
J. Mater. Chem., 1998, 8(11), 2357–2369
2363

of the carboximide functions, and do not result from chemical
modification or from aggregation of the chromophores.
In a semiquantitative analysis, the radiative lifetime t
,
FM
defined as the reciprocal of the radiative transition probability,
can be estimated from the Strickler–Berg35 equation, which
for dilute solutions becomes eqn. (1),
Photophysical behavior. Based on the remakably large quan-
tum yield of fluorescence (w ) of perylene 1a and terrylene 7a
approaching unity in solution,15,34 one would have expected
that quaterrylenebis(dicarboximide) 2b will, to some degree,
emit light in the NIR window. However, no luminescence
could be detected for quaterrylenebis(dicarboximide) 2b in
f
1
e(v)
˜
=2.88×10−9 n2 ꢀv−3ꢁ−1
dv
˜
(1)
˜
P
t
v
˜
FM
where n is the refractive index and ꢀv−3ꢁ−1 is the reciprocal
˜
of an appropriate average over the fluorescence spectrum
defined in eqn. (2).
dilute solutions. Similarly, a dramatic decrease of w has been
f
observed for quaterrylenebis(dicarboximide) 6c (w =0.05) in
f
comparison with perylene 6a and terrylene 6b.14 Remarkably
F(v)dv
enough, it was recently discovered that the lack of emission
of 2b is related to traces of unknown impurities. Normally,
samples of quaterrylenebis(dicarboximide) 2b purified by
column chromatography on silica gel with methylene chloride
as eluent and precipitation in methanol, do not emit in
chloroform solution, even though no impurities were observed
by 1H NMR and UV–VIS–NIR spectroscopy, FD-MS, and
thin layer chromatography. Nevertheless if quaterrylenebis-
(dicarboximide) 2b is further purified by several extractions in
ethyl acetate, an emission centered at 797 nm in chloroform
solution is observed (Fig. 5). Characteristically, the emission
P
ꢀv−3ꢁ−1 =
˜
(2)
F(v)dv
v3
P
The essential values needed eqn. (1) and (2) can be inferred
from the absorption spectrum as well as from the steady state
PL spectrum. Insertion of these parameters then leads to a
radiative lifetime of about t =65 ns.
Further information about the photophysical properties of
quaterrylenebis(dicarboximide) 2b are given by time resolved
photoluminescence measurements. In Fig. 6(a) a transient of
the PL detected at the PL maximum at 800 nm is displayed.
The measurement shows a monoexponential decay with a
surprisingly short fluorescence decay time of about 320 ps. All
transients taken at different wavelength of the PL spectrum
exhibit exactly the same time dependence, as can be seen from
FM
maxima [l (em)] of quaterrylenebis(dicarboximide) 2b
max
extends to even longer wavelength in the NIR window than
those of terrylenebis(dicarboximide) 7a [l (em)=673 nm],
max
(em)=701 nm] and perylenebis-
(em)=768 nm].15,16
benzoylterryleneimide 8a [l
max
amidine 9 [l
max
In Fig. 5 the absorption as well as the steady state photo-
luminescence (PL) are shown for the sake of comparison. The
ground state absorption spectrum shows a strong inhomo-
geneously broadened S –S (0–0) transition centered at 763 nm
0
1
followed by inhomogeneously broadened vibronic satellites
centered at 695 and 626 nm, respectively. Deconvolution of
the ground state absorption spectrum with Gaussian profiles
allows the estimation of the absorption coefficient e as well as
the oscillator strength f of the observed transitions. The molar
extinction coefficients for the optical transitions are e=
90000 cm2 mol−1, corresponding to an oscillator strength of
about f=0.9, and e=51700 cm2 mol−1, relating to f=0.67,
for the pure electronic (0–0) and the dominant vibronic (0–1)
transitions, respectively. The dominant vibrational mode is
energetically offset by about 1300 cm−1, indicating a ring
breathing mode. Comparing the transition intensities of the
pure electronic transition with the ones of the vibronic trans-
itions, it becomes evident that the quaterrylenebis(dicarboxim-
ide) 2b is a very rigid material showing a slight distortion in
the excited state only. Furthermore, the slight deviations from
mirror symmetry indicate only minor differences in the nuclear
configurations of the ground and the excited state. Therefore,
we conclude that the large Stokes shift (about 35 nm) observed
in emission is mainly due to solvation effects.
Fig. 6 (a) Time dependence behaviour of the emission detected at
800 nm after excitation with 100 fs pulses. (b) Semilogarithmic plot of
PL decays monitored at different detection energies.
Fig. 5 Absorption and emission spectra of quaterrylenebis(dicarboxi-
mide) 2b in CHCl . The photoluminescence excitation is at 740 nm.
3
2364
J. Mater. Chem., 1998, 8(11), 2357–2369

Fig. 6(b), in which the transients are displayed on a semi-
logarithmic scale.
the perylenebis(dicarboximide) 1b, the terrylenebis(dicarboxi-
mide) 7b, and the quaterrylenebis(dicarboximide) 18 do not
differ significantly.
This proves that no time and energy dependent rate, e.g.
filling process, is involved in the radiative transition. However,
the decay time seems to be surprisingly short compared to
other members of this molecular family. Following the work
on radiationless transitions in molecules one can roughly
estimate that the probability of nonradiative transitions
increases exponentially with decreasing energy gap DE between
the potential minima for the state involved [eqn. (3)],36
Photochemical stability. The photostability of quaterrylene-
bis(dicarboximide) 2b has been estimated by exposing under
air a polystyrene film of roughly 10 mm containing 0.5 wt% of
dyes to UV light (l=366 nm) for a prolonged period of time.15
After 10 days of irradiation, no significant alteration of the
absorption spectrum could be observed, demonstrating the
photochemical inertness of quaterrylenebis(dicarboximide) 2b
in a polymer matrix.
cDE
k 3exp
nr
−
(3)
A
2phv
B
Conclusions
where v is the vibrational frequency and c is a quantity
expressible in terms of molecular parameters. By comparing
quaterrylenebis(dicarboximide) with perylene on the basis of
this expression and taking into account that the main excess
energy is dissipated through C–H vibrational modes (ca.
300 cm−1) an increase of the nonradiative transition prob-
ability of roughly a factor 25 can be estimated, which concurs
The synthesis of three quaterrylenebis(dicarboximide)s 2a,b,
18 and 23 differing by their substitution pattern has been
achieved. The extension of the p-system of the quaterrylenebis-
(dicarboximide)s 2a,b, 18 and 23, in comparison to the
perylenebis(dicarboximide)s 1, has several intriguing conse-
quences for their photophysical and electrochemical properties.
Firstly, the quaterrylenebis(dicarboximide)s 2a,b, 18 and 23
are characterized by an intense absorption in the NIR, between
750 and 800 nm in chlorinated solvents, whereas the absorption
of perylenebis(dicarboximide)s 1 ranges between 520 and
590 nm. Secondly, the quaterrylenebis(dicarboximide) 2b pre-
sents an emission centered at 797 nm with a quantum efficiency
estimated at 5%, which is significantly lower than those of
perylenebis(dicarboximide)s 1 which approach one. Thirdly,
a definite stabilization of the tri- and tetra-anion of the
quaterrylenebis(dicarboximide) 18 occurs, whereas little
difference is observed between the two first reduction potentials
of 18 and 1b. Fourthly, the quaterrylenebis(dicarboximide)
2b exhibits, in strongly acidic solvents, an extremly intense
absorption around 900 nm. However, this intense absorption
cannot be explained by the formation of J-aggregates in
solution, and is more likely caused by the protonation of the
carboximide functions.
fairly well with the PL decay time of t =320 ps measured.
FM
Moreover, by insertion of the values obtained throughout the
analysis above the quantum efficiency expressed as Q=t/t
can be estimated to approximatively 5%.
FM
Electrochemical behavior. The reduction potentials of substi-
tuted perylenebis(dicarboximide) 1b and quaterrylenebis-
(dicarboximide) 18 are collected in Table 3. The cyclic voltam-
mogram (CV) shows a four-fold reduction of the quaterrylene-
bis(dicarboximide)s 18. The first two electrons are localized
on the carbonyl groups because only a small difference is
observed for the first (−0.74 V) and second reduction poten-
tials (−1.10 V) of quaterrylenebis(dicarboximide) 18 as com-
pared to the smaller homologue, perylenebis(dicarboximide)
1b, at −0.85 and −1.11 V, respectively. This suggests that the
two first reduction potentials are independent of the size of
the conjugated p-system, indicating that the electrons go in to
the quaterrylenebis(dicarboximide) 18 and the perylenebis-
(dicarboximide) 1b in two different locations, presumably at
the two imide functions, without appreciable interaction.37
In contrast, a definite charge stabilization, due to the
extension of the p-system of the quaterrylenebis(dicarboxim-
ide) 18 in comparison to the perylene 1b, is observed for the
reduction to the tri- and tetra-anion. The third reduction
potential of the quaterrylenebis(dicarboximide) 18 (−1.97 V)
has a much lower absolute value than the one of the
corresponding perylenebis(dicarboximide) 1b (−2.64 V).
Remarkably enough, a fourth reduction is observed for the
quaterrylenebis(dicarboximide) 18. Moreover, this fourth
reduction potential lies at −2.26 V, i.e. 0.38 V lower than the
third reduction potential of perylenebis(dicarboximide) 1b.
In addition to these new photophysical and electrochemical
properties the quaterrylenebis(dicarboximide)s 2a,b, 18 and
23 also display good chemical, photochemical and thermal
stability. Clearly, this unusual ensemble of properties qualifies
the quaterrylenebis(dicarboximide)s 2a,b and 18 as functional
NIR materials and suggests the synthesis of even larger
rylenebis(dicarboximides) dyes.
We gratefully acknowledge the financial support of BASF AG
and the Bundesministerium fur Forschung und Technologie.
¨
Experimental
Spectral data were obtained on Nicolet FT-IR 320 (IR),
Perkin-Elmer Lambda 9 and 15 (UV–VIS), Varian Gemini
200, Bruker AC 300 or AMX 500 (NMR), Potentiostat/
Galvanostat PAR Model 173 (CV), Finnigan MAT 312 (FD-
MS) and Mettler TG 50 (TGA) instruments. For the cyclovol-
tammetric experiments with 18 (in THF, with Bu NPF added)
Thermal stability. Thermogravimetric analyses (TGA) con-
ducted under nitrogen atmosphere show that quaterrylenebis-
(dicarboximide) 18 possesses a high thermal stability. The first
weight loss is observed between 485 and 500 °C and corre-
sponds to the cleavage of the isopropyl groups. In this respect,
4
6
a Potentiostat/Galvanostat PAR Model 173 was used. The
setup for photoluminescence consisted of an XeCl excimer
pumped dye laser system (15 Hz rep. rate and 10 ns pulse
width) running at 740 nm. The emission from the sample was
collected and focussed into the entrance slit of a 270 cm grating
monochromator fitted with a charge coupled device (CCD)
array for detection. Fluorescence lifetime measurements were
performed with an Kerr-lens mode-locked Ti5sapphire laser
operating at 740 nm and producing 100 fs pulses at a repetition
rate of 80 MHz. Here, as in the time integrated experiments,
the emission was dispersed in a monochromator and monitored
by a streak camera to follow the potoluminescence decay with
a time resolution of about 6 ps. All measurements were
performed at room temperature. The photostability tests were
Table 3 Reduction potentials versus saturated calomel electrode of
perylenebis(dicarboximide) 1b and quaterrylenebis(dicarboximide) 18
in tetrahydrofuran at 0 °C
E/V vs. SCE
Charge
Perylene 1b
Quaterrylene 18
−1
−2
−3
−4
−0.85
−1.11
−2.64
—
−0.74
−1.10
−1.97
−2.26
J. Mater. Chem., 1998, 8(11), 2357–2369
2365

conducted with a UV lamp (Camag, 0.25 A, 220 V), placing
the polystyrene films 12 cm away from the lamp. The
melting points (mp) are reported uncorrected. All solvents
N-Dodecyl-9-bromoperylene-3,4-dicarboximide 12a
2.5 g (5.1 mmol) N-Dodecylperylene-3,4-dicarboximide 11a
were dissolved in 750 ml methylene chloride and a catalytic
amount of iron powder was added. After 15 min, 8 g
(50 mmol) of bromine in 50 ml methylene chloride were added
to the reaction mixture. The temperature was slowly increased
and the reaction mixture was refluxed for 3 h. After cooling
to room temperature, the excess bromine and most of the
methylene chloride were evaporated under vacuum. The
resulting concentrated solution was poured into a large volume
of methanol and this solution was stored at −20 °C for 1 h.
The resulting precipitate was filtered and washed with plenty
of methanol. Drying under vacuum afforded 2.73 g of the title
compound 12a as a red powder (94% yield).
for reactions were distilled before use. Ni(cod) was pur-
2
chased from Strem Chemicals, all other chemicals were
purchased from Aldrich and used as received. 3,4,9,10-
Perylenetetracarboxylic dianhydride and N-(2,6-diisopro-
pylphenyl)perylene-3,4-dicarboximide (11b) were obtained
from BASF AG. The N-propyl-1,657,12-tetra(4-hexyloxy-
phenoxy)perylene-3,459,10-bis(dicarboximide) (19) has been
previously described in the literature.17,25
N-Dodecylperylene-3,4,9,10-tetracarboxylic acid 3,4-anhydride
9,10-dicarboximide§
d
(500 MHz, C D Cl , 135 °C) 8.6–8.5 (m, 2H, H-2,5),
15.0 g (38 mmol) 3,4,9,10-Perylenetetracarboxylic dianhydride
and 84.0 g (0.45 mmol) dodecylamine were added to a mixture
of 1 L propan-1-ol and 0.5 L water. The reaction mixture was
stirred at 65 °C for 7 h. After cooling to room temperature,
150 mL of concentrated HCl were added to the reaction
mixture and 1 L of water was added. The precipitate was
separated from the liquid phase by centrifugation and dried
under vacuum, affording 20 g of the title compound as an
orange powder (94% yield). N-Dodecylperylene-3,4,9,10-
tetracarboxylic acid 3,4-anhydride 9,10-dicarboximide 10a was
used directly for the next reaction without further purification.
For characterization purposes, a small amount was purified
by chromatography on silica gel with chloroform as eluent.
H
2 2 4
8.5–8.3 (m, 4H, H-12,7,1,6), 8.15 (d, 1H, H-10), 7.90 (d, 1H,
H-8), 7.71 (dd, 1H, H-11), 4.23 (t, 2H, a-CH ), 1.84 (m, 2H,
b-CH ), 1.48 (m, 2H, c-CH ), 1.35 [br, 16H, (CH ) ], 0.94 (t,
2
2
2
2 8
3H, CH ); n /cm−1 2954, 2921, 2870, 2851, 1694 (CNO),
3
max
1651 (CNO), 1616, 1594, 1562, 1497, 1467, 1455, 1383, 1359,
1333, 1296, 1244, 812, 805, 751; l (CH Cl )/nm (e) (absorp-
max
2 2
tion) 255 (18930), 263 (34690), 480 (31240), 504 (32090); m/z
(FD) 569.4 (M+, 100%) [C H NO Br (568.55 g mol−1)
34 34
2
calc.: C, 71.83; H, 6.03; N, 2.46; Br, 14.05. Found: C, 70.59;
H, 5.71; N, 2.40; Br, 14.21%]; mp 231 °C.
N-(2,6-Diisopropylphenyl)-9-bromoperylene-3,4-dicarboximide
12b
d
(300 MHz, C D Cl , 135 °C) 8.68 (d, 2H, H-8,11), 8.66
H
2 2 4
(d, 2H, H-2,5), 8.60 (d, 2H, H-7,12), 8.59 (d, 2H, H-1,6), 4.20
10 g (21 mmol) N-(2,6-diisopropylphenyl)perylene-3,4-dicar-
boximide 11b were dissolved under slight heating in 1 L
chlorobenzene. Bromine (15 g, 95 mmol) was added and the
reaction mixture was stirred for 4.5 h at 50 °C. Chlorobenzene
and unreacted bromine were removed under vacuum. The
resulting solid was recrystallised from methylene chloride–
methanol, yielding 11.4 g (98%) of the title compound 12b.
(t, 2H, a-CH ), 1.79 (m, 2H, b-CH ), 1.41 (m, 2H, c-CH ),
2
2
2
1.28 [br, 16H, (CH ) ], 0.87 (t, 3H, CH ); n /cm−1 2954,
2 8
3
max
2924, 2850, 1765 (CNO), 1743, 1724 (CNO), 1697 (CNO),
1656 (CNO), 1616, 1595, 1580, 1508, 1434, 1407, 1350, 1340,
1324, 1297, 1274, 1253, 1241, 1153, 1127, 1033, 1018, 866,
810, 739; l (H SO )/nm (e) (absorption) 390 (8170), 544
max
2
4
(42800), 581 (60440); m/z (EI) 559.3 (M+, 86%), 405.2
d
(300 MHz, CDCl , 30 °C) 8.64 (d, 1H, H-2), 8.62 (d,
H
3
(M+−C H , 24%), 392.2 (M+−C H , 100%), 248.2
1H, H-5), 8.45 (d, 1H, H-1), 8.42 (d, 1H, H-6), 8.37 (d, 1H,
H-12), 8.27 (d, 1H, H-7), 8.20 (d, 1H, H-10), 7.87 (d, 1H, H-
8), 7.69 (t, 1H, H-11), 7.47 (dd, 1H, H-16), 7.33 (d, 2H, H-
15), 2.77 [m, 2H, CH(CH ) ], 1.18 [d, 12H, CH(CH ) ]; d
11 22
12 24
(perylene+, 60%) (calc. M+, 558.7); mp >300 °C.
N-Dodecylperylene-3,4-dicarboximide 11a
3 2
3 2
C
(125.5 MHz, CDCl , 30 °C) 163.85, 145.69, 136.90, 136.77,
133.02, 132.09, 132.02, 131.31, 130.94, 130.43, 130.08, 129.66,
129.44, 129.21, 129.11, 128.21, 126.69, 126.20, 124.47, 123.98,
5.0 g (8.9 mmol) 10a and 200 mL of a 12 wt% KOH solution
were introduced into a 250 mL autoclave. The temperature
was raised to 230 °C for 18 h. After cooling to room tempera-
ture, the resulting precipitate was filtered off, washed with
plenty of water and dried under vacuum. The resulting solid
was extracted with diethyl ether and precipitated in a large
volume of methanol. Then the red powder was dried under
vacuum to afford 3.25 g of the title compound (75% yield).
N-Dodecylperylene-3,4-dicarboximide 11a was used directly
for the next reaction without further purification. For charac-
terization purposes a small amount (500 mg) was purified by
column chromatography on silica gel with toluene as eluent.
3
123. 81, 121.43, 120.75, 120.48, 29.13, 23.96; n /cm−1 1701
max
(CNO), 1660 (CNO); l (CH Cl )/nm (e) (absorption) 263
max
2 2
(34056), 355 (3065), 484 (34762), 509 (35319); (fluorescence)
540; m/z (FD) 561.1 (M+, 100%) [C H NOBr
34 26
(560.49 g mol−1) calc.: C, 72.86; H, 4.68; N, 2.50; Br, 14.26.
Found: C, 71.93; H, 4.71; N, 2.50; Br, 13.77%]; mp >300 °C.
R (silica gel) 0.45 (CH Cl ), 0.09 (toluene).
f
2 2
N-(2,6-Diisopropylphenyl)-9-(tributylstannyl)perylene-3,4-
dicarboximide 13b
d
(300 MHz, CDCl , 30 °C) 8.49 (d, 2H, H-2,5), 8.32 (d,
H
3
2H, H-7,12), 8.29 (d, 2H, H-1,6), 7.83 (d, 2H, H-9,10), 7.55
13.5 g (24 mmol) of the monobromoperylene 12b, 26.3 g
(45 mmol) hexabutylditin and 0.1 g (0.1 mmol, 0.3 mol%)
Pd(PPh ) were refluxed in 700 ml toluene for 4 days. The
solvent was removed under vacuum. Purification was carried
out by column chromatography on silica gel with CH Cl as
eluent, affording 16 g of the title compound as a red solid
(dd, 2H, H-8,11), 4.16 (t, 2H, a-CH ), 1.77 (m, 2H, b-CH ),
2
2
1.42 (m, 2H, c-CH ), 1.28 [br, 16H, (CH ) ], 0.87 (t, 3H,
2 8
CH ); d (75.5 MHz, CDCl , 30 °C) 163.89 (C=O), 137.25,
2
3 4
3
C
3
134.74, 131.45, 130.85, 129.68, 128.37, 127.21, 123.72, 121.71,
120.36, 40.74, 32.00, 29.73, 29.70, 29.52, 29.36, 28.45, 27.43,
2
2
22.67, 13.96; n /cm−1 2956, 2916, 2850, 1691 (CNO), 1652
(88% yield).
max
(CNO), 1595, 1571, 1469, 1381, 1354, 1295, 1262, 1249, 1105,
d
(500 MHz, CDCl , 30 °C) 8.66 (d, 1H), 8.65 (d, 1H),
H
3
1079, 1032, 1022, 813, 762, 753; l (CH Cl )/nm (e) (absorp-
8.50 (d, 1H), 8.47 (d, 1H), 8.46 (d, 1H), 8.40 (d, 1H), 7.88
(d, 1H), 7.84 (d, 1H), 7.69 (t, 1H), 7.49 (t, 1H), 7.35 (d, 2H),
2.79 (h, 2H), 1.69–1.56 (m, 6H), 1.44–1.33 (m, 6H), 1.31–1.27
(m, 6H), 1.20 (d, 12H), 0.92 (t, 9H); d (125.5 MHz, C D Cl ,
max
2 2
tion) 263 (33100), 480 (28810), 502 (28330); m/z (FD) 489.3
(M+, 100%), 978.3 (M2+, 77%) [C H NO (489.66 g mol−1)
34 35
2
calc.: C, 83.40; H, 7.21; N, 2.86. Found: C, 82.87; H, 7.04; N,
C
2 2 4
30 °C) 164.0, 149.7, 145.7, 140.1, 138.0, 137.7, 136.3, 133.4,
132.0, 131.1, 130.5, 129.8, 129.4, 129.2, 127.0, 126.8, 124.0,
123.7, 122.7, 120.8, 120.0, 119.9, 29.3, 29.2, 27.3, 24.0,
2.71%]; mp 179 °C.
§IUPAC name: N-dodecyl-13,15-dioxo-9,10-(methanoepiminometh-
ano)perylene-3,4-dicarboxylic anhydride
13.6, 10.8; n (KBr)/cm−1 1699 (CNO), 1663 (CNO);
max
2366
J. Mater. Chem., 1998, 8(11), 2357–2369

l
(CHCl )/nm (e) (absorption) 267 (4.45), 496 (4.56), 521
added in a 250 ml Schlenk flask under argon. The reaction
mixture was vigorously stirred at 120 °C for 2.5 h. After
cooling to room temperature, the solidified solution was
dissolved in water and poured into 500 mL water–hydrochloric
acid (551). The resulting precipitate was filtered and dried
under vacuum. Purification was carried out by extraction using
max
3
(4.54); m/z (FD) 772.5 (M+, 100%) calc. M+, 772.5); mp
158–159 °C.
N,N∞-Bis(dodecyl)-9,9∞-biperylene-3,453∞,4∞-bis(dicarboximide)
14a
CHCl as solvent until no colored side product could be
extracted. Drying the resulting dark blue powder afforded
369 mg of the title compound (83% yield).
Ni(cod) (180 mg, 0.67 mmol), cyclooctadiene (600 mg,
5.6 mmol) and 2,2∞-bipyridyl (105 mg, 0.67 mmol) were added
3
2
to 80 ml DMF in a 100 ml Schlenk flask under argon. The
mixture was stirred at room temperature for 1 h and bromo-
perylenedicarboximide 12a (382 mg, 0.67 mmol) was added to
the purple solution. After 36 h at 65 °C, the reaction mixture
was cooled to room temperature and poured into 120 mL
water–hydrochloric acid–methanol (15152). The resulting pre-
cipitate was filtered off, washed with water and dried under
vacuum, yielding 293 mg (89%) of the title compound 14a as
a deep red powder.
d (CP MAS TOSS, 4.5 kHz) 161.54 (CNO), 140–115 (C,
C
aromatic), 40.60, 30.75, 23.43, 14.42; l /cm−1 2921, 2851,
max
1690 (CNO), 1650 (CNO), 1594, 1575, 1548, 1502, 1455,
1430, 1404, 1382, 1354, 1288, 1244, 1126, 1115, 810;
l
(H SO )/nm (e) 208 (0.375), 374 (0.055), 622 (0.170),
max
858 (0.219), 896 (0.419), 989 (0.469), 1134 (0.021); l
max
[H SO –oleum (57%) (451)]/nm (e) 281 (524300), 323 (57700),
2
4
2
4
784 (34400), 876 (337000); m/z (FD) 974.2 (M+, 100%) (calc.
M+, 975.3); mp >300 °C.
d
(500 MHz, C D Cl , 135 °C) 8.53 (2d, 4H, H-5,2), 8.38
H
2 2 4
(d, 2H, H-7), 8.32 (d, 2H, H-6), 8.28 (2d, 4H, H-1,12), 8.12
(d, 2H, H-8), 7.88 (d, 2H, H-10), 7.69 (t, 4H, H-11), 4.22 (t,
4H, a-CH ), 1.81 (m, 4H, b-CH ), 1.48 (m, 4H, c-CH ), 1.34
N,N∞-(2,6-Diisopropylphenyl)quaterrylene-3,4513,14-bis-
(dicarboximide) 2b
2
2
2
[br, 32H, (CH ) ], 0.94 (t, 6H, CH ); d (125.5 MHz, C D Cl ,
N,N∞-Bis(2,6-diisopropylphenyl)-9,9∞-biperylene-3,453∞,4∞-bis-
(dicarboximide) (750 mg, 0.78 mmol), 80 g KOH and 6 g
glucose, were added in a 250 ml Schlenk flask under argon.
The reaction mixture was vigorously stirred at 120 °C for 2.5 h.
After cooling to room temperature, the solidified solution was
dissolved in water and poured into 500 mL water–hydrochloric
acid (551). The resulting precipitate was filtered and dried
under vacuum. Purification was carried out by column chroma-
tography on silica gel using CH Cl as eluent. Precipitation
2 8
3
C
2 2 4
135 °C) 164.85, 164.84, 137.58, 137.45, 134.40, 132.59, 132.56,
132.53, 131.10, 131.08, 130.94, 130.52, 130.50, 129.41, 127.71,
127.23, 125.44, 124.75, 123.12, 123.10, 121.94, 121.66, 41.91,
33.14, 30.87, 30.84, 30.82, 30.65, 30.50, 29.55, 28.55, 23.83,
15.16; n /cm−1 2955, 2923, 2852, 1696, 1651, 1594, 1563,
max
1497, 1384, 1359, 1245, 805, 750; l (CH Cl )/nm (e) (absorp-
max
2 2
tion) 263 (56150), 481 (51030), 504 (53160); m/z (FD) 977.3
(M+, 100%) [C H N O (977.30 g mol−1) calc.: C, 83.57;
68 68 2 4
2
2
H, 7.01; N, 2.87. Found: C, 83.09; H, 7.11; N, 2.92%];
from CH Cl in methanol afforded 620 mg of the title com-
2
2
mp 204 °C.
pound as a green powder (83% yield).
d (300 MHz, C D Cl , 135 °C) 8.68 (d, 4H, H-2, 5, 12, 15),
H
2 2 4
N,N∞-Bis(2,6-diisopropylphenyl)-9,9∞-biperylene-3,453∞,4∞-
8.68, 8.63 (d, 4H, H-7, 10, 17, 20, 8, 9, 18, 19), 8.56 (d, 4H,
H-1, 6, 11, 16), 7.42 (dd, 2H, Ph-H-24), 7.29 (d, 4H, Ph-H-
23), 2.80 [m, 4H, CH(CH ) ], 1.19 [d, 24H, CH(CH ) ];
bis(dicarboximide) 14b
Ni(cod) (496 mg, 1.78 mmol), cod (161 mg, 1.48 mmol) and
3 2
3 2
2
n
/cm−1 1702 (CNO), 1659 (CNO); l (CH Cl )/nm
2,2∞-bipyridyl (278 mg, 178 mmol) were added to 80 ml DMF
max
max
2 2
(e)264 (97377), 274 (100124), 317 (9195), 375 (14689), 764
in a 100 ml Schlenk flask under argon. The mixture was stirred
at room temperature for 1 h and bromoperylenedicarboximide
(1 g, 1.78 mmol) was added to the purple solution. After two
days at 70 °C, the reaction mixture was cooled to room
temperature and poured into 1 L water–hydrochloric acid
(551). The precipitate was filtered off, washed with water,
dried under vacuum and purified by silica gel column chroma-
tography using CH Cl as eluent. Solvent was evaporated
(162024);
l
[H SO –oleum (59%) (451)]/nm (e)281
max
2
4
(698994), 326 (58801), 783 (83173), 876 (654705); m/z (FD)
479.2 (M2+, 37%), 958.5 (M+, 100%), (calc. M+, 959.1); mp
>300 °C; R (silica gel) 0.02 (CH Cl ), 0.81 (THF).
f
2 2
N-(2,6-Diisopropylphenyl)-1,6,9-tribromoperylene-3,4-
dicarboximide 15
2
2
under vacuum, then the resulting solid was redissolved in a
minimum of CH Cl and a large excess of methanol was
To a solution of N-(2,6-diisopropylphenyl)perylene-3,4-dicar-
boximide 11 (12 g, 25 mmol) in 1.5 L chloroform, 70 mL of
bromine were added and the reaction mixture was refluxed for
6 h. After cooling to room temperature, the reaction mixture
was washed with a solution of 15 g KOH and 10 g sodium
sulfite in 2 L water. The organic layer was separated and dried
on magnesium sulfate. Removing the solvent under vacuum
afforded 19.5 g of the title compound as an orange solid. The
purity was found to be sufficient for the next reaction. For
analytical purposes, 2 g of the orange solid were purified by
column chromatography on silica gel using CH Cl as eluent.
2
2
added. The green precipitate was filtered, washed with meth-
anol and dried under vacuum, yielding 710 mg (83%) of the
title compound 14b.
d
(300 MHz, CDCl , 30 °C) 8.72 (d, 2H, H-5), 8.70 (d,
H
3
2H, H-2), 8.65 (d 2H, H-7), 8.58 (d, 2H, H-6), 8.50–8.55 (m,
4H, H-12,1), 7.74 (d, 2H, H-8), 7.62 (d, 2H, H-10), 7.55 (d,
2H, H-11), 7.48 (dd, 2H, Ph-H-16), 7.34 (d, 4H, Ph-H-15),
2.78 [m, 4H, CH(CH ) ], 1.18 [d, 24H, CH(CH ) ]; d
(125.5 MHz, CDCl , 30 °C) 163.95, 145.74, 145.71, 140.53,
137.44, 137.23, 135.30, 133.71, 132.13, 130.99, 130.57, 129.65,
3 2
3 2
C
3
2
2
Precipitation from CH Cl in methanol afforded 1.67 g of the
title compound (91% yield).
2
2
129.59, 129.48, 129.37, 129.27, 128.32, 127.47, 127.01, 124.08,
124.04, 123.40, 121.34, 121.29, 120.61, 120.47, 29.17, 24.03;
d (500 MHz, CDCl , 30 °C) 9.33 (d, 1H, H-12), 9.11 (d,
H
3
n
/cm−1 1702 (CNO), 1662 (CNO); l (CH Cl )/nm (e)
1H, H-7), 8.94 (s, 1H, H-2), 8.93 (s, 1H, H-5), 8.45 (d, 1H,
H-10), 7.99 (d, 1H, H-8), 7.80 (t, 1H, H-11), 7.51 (t, 1H, Ph-
max
max
2 2
(absorption) 264 (57790), 355 (6503), 499 (66477), 528
(83055); (fluorescence) 597; m/z (FD) 480.8 (M2+, 29%),
H-16), 7.36 (d, 2H, Ph-H-15), 2.73 [heptet, 2H, CH(CH ) ],
3 2
960.8 (M+, 100%) [C H N O (961.17 g mol−1) calc.: C,
68 52 2 4
1.20 [d, 12H, CH(CH ) ]; d (125.5 MHz, CDCl , 30 °C)
3 2
c
3
84.97; H, 5.45; N, 2.91. Found: C, 84.02; H, 5.39; N, 2.70%];
162.54, 145.63, 135.37, 135.15, 134.56, 131.62, 130.92, 130.69,
130.33, 130.28, 129.82, 129.78, 129.58, 128.86, 128.75, 127.53,
126.94, 126.91, 126.74, 126.50, 124.14, 120.94, 120.89, 119.24,
mp >300 °C; R (silica gel) 0.12 (CH Cl ), 0.84 (THF).
f
2 2
N,N∞-Bis(dodecyl)quaterrylene-3,4513,14-bis(dicarboximide)
2a
119.02, 29.25, 23.98; n (KBr)/cm−1 1711 (CNO), 1672
max
(CNO); l (CH Cl )/nm (e) 228 (78697), 281 (28194), 379
max
2 2
N,N∞-Bis(dodecyl)-9,9∞-biperylene-3,453∞,4∞-bis(dicarboximide)
(977 mg, 1 mmol), 100 g KOH, 4 g glucose and 100 mL were
(3116), 401 (3398), 513 (33013); m/z (FD) 719.0 (M+, 100%)
[C H NO Br (718.27 g mol−1) calc.: C, 56.86; H, 3.37; N,
34 24
2
3
J. Mater. Chem., 1998, 8(11), 2357–2369
2367

1.95; Br, 33.37. Found: C, 56.49; H, 3.42; N, 1.72; Br, 32.01%];
methanol afforded 421 mg of quaterrylenebis(dicarboximides)
18 as a green powder (85% yield).
mp >300 °C; R (silica gel) 0.77 (CH Cl ), 0.48 (toluene).
f
2 2
d (500 MHz, CDCl , 30 °C) 9.09 (d, 4H, H-7, 10, 17, 20),
H
3
8.32 (s, 4H, H-2, 5, 12, 15), 7.76 (d, 4H, H-8, 9, 18, 19), 7.41
(t, 2H, Ph-H-24), 7.34 (d, 8H, Ph-H-24), 7.28 (d, 4H, Ph-H-
N-(2,6-Diisopropylphenyl)-1,6-bis(4-tert-butylphenoxy)-9-
bromoperylene-3,4-dicarboximide 16
23), 7.00 (d, 8H, Ph-H-2), 2.76 [m, 4H, CH(CH ) ], 1.26 (s,
3 2
N-(2,6-Diisopropylphenyl )-1,6,9-tribromoperylene-3,4-dicarb-
oximide 15 (16 g, 22 mmol), 4-tert-butylphenol (6.6 g,
0.044 mol) and potassium carbonate (6.9 g, 0.05 mol) were
stirred in 500 ml NMP at 120 °C for 6 h. After cooling to
room temperature, the reaction mixture was poured into 2 l
water–HCl (551). The resulting precipitate was filtered,
washed with water and dried under vacuum. The desired
product was purified by column chromatography on silica gel
using CH Cl as eluent. Precipitation from CH Cl into meth-
36H, tert-butyl ), 1.13 [d, 24H, CH(CH ) ]; d (125.5 MHz,
3 2
C
CDCl , 30 °C) 162.99, 153.55, 152.93, 147.00, 145.75, 131.24,
130.85, 130.80, 129.40, 129.19, 128.87, 127.73, 127.47, 127.17,
3
126.42, 125.24, 124.32, 123.94, 122.53, 121.63, 117.39, 34.37,
31.44, 29.23, 24.10; n (KBr)/cm−1 1707 (CNO), 1669
max
(CNO); l (CH Cl )/nm (e) (absorption) 262 (95819), 271
max
2 2
(97645), 382 (12895), 709 (71931), 781 (166571); (fluores-
cence) 806; m/z (FD) 775.2 (M2+, 38%), 1551.3 (M+, 100%)
(calc. M+, 1552.0); mp >300 °C; R 0.43 (CH Cl ), 0.03
(toluene).
2
2
2
2
f
2 2
anol afforded 6.28 g of the title compound as a red powder
(33% yield).
d (300 MHz, CDCl , 30 °C) 9.40 (d, 1H, H-12), 9.16 (d,
N-Propyl-1,6,7,12-tetra(4-hexyloxyphenoxy)perylene-3,4-
dicarboximide 20
H
3
1H, H-7), 8.35 (d, 1H, H-10), 8.34 (s, 1H, H-2), 8.32 (s, 1H,
H-5), 7.88 (d, 1H, H-8), 7.69 (t, 1H, H-11), 7.4–7.5 (m, 5H,
Ph-H-16,3,3∞), 7.30 (d, 2H, Ph-H-15), 7.08 (m, 4H, Ph-H-
N-Propyl-1,6,7,12-tetra(4-hexyloxyphenoxy)perylene-3,459,10-
bis(dicarboximide) 19 (15 g, 12 mmol) and 150 g KOH were
added to 1 L of propan-2-ol. The reaction mixture was refluxed
for 105 min. After cooling to room temperature, 2.5 L water
and 250 ml of concentrated hydrochloric acid were added. The
resulting precipitate was filtered, washed with water and dried
under vacuum. The crude product was then dissolved in a
2,2∞), 2.72 [m, 2H, CH(CH ) ], 1.35 (s, 18H, tert-butyl), 1.15
3 2
[d, 12H, CH(CH ) ]; d (125.5 MHz, CDCl , 30 °C) 163.14,
3 2
C
3
153.80, 153.69, 153.17, 153.10, 147.35, 147.33, 145.64, 132.00,
131.54, 131.01, 130.87, 130.67, 129.42, 129.32, 129.29, 128.68,
128.05, 127.83, 127.55, 127.18, 126.63, 126.54, 125.35, 124.36,
124.30, 123.91, 123.02, 121.89, 121.87, 118.43, 118.36, 34.43,
suspension of 25 g Cu O in 800 ml quinoline. The temperature
31.45, 29.09, 23.99; n (KBr)/cm−1 1706 (CNO), 1670
2
max
was raised to 240 °C under vacuum and 500 ml quinoline were
(CNO); l (CH Cl )/nm (e) 274 (40081), 420 (9949), 513
max
2 2
distilled over a period of 6 h. The reaction mixture was cooled
to room temperature, and 2.5 L water and 150 mL concen-
trated hydrochloric acid were added. The resulting precipitate
was filtered, washed with water and dried under vacuum.
Purification was carried out by chromatography on silica gel
with toluene as eluent. The second fraction was identified as
the title compound. Precipitation in methanol afforded 5.70 g
of the title compound as a red–orange powder (42% yield).
d (300 MHz, CDCl , 30 °C) 8.10 (s, 2H, H-2, 5), 7.72 (d,
(41553); m/z (FD) 855.2 (M+, 100%) [C H NO Br
54 50
4
(856.90 g mol−1): calc.: C, 75.69; H, 5.88; N, 1.63; Br, 9.32.
Found: C, 75.27; H, 5.92; N, 1.41; Br, 8.69%]; mp 297 °C; R
f
0.86 (CH Cl ), 0.56 (toluene).
2
2
N,N∞-Bis(2,6-diisopropylphenyl)-1,1∞,6,6∞-tetra(4-tert-
butylphenoxy)-9,9∞-biperylene-3,453∞,4∞-bis(dicarboximide) 17
770 mg (2.8 mmol) Ni(cod) , 252 mg (2.34 mmol) cod,
H
3
2
2H, H-9, 10), 7.09 (d, 2H, H-8, 11), 6.7–7.0 (m, 16H, Ph-H),
4.08 (t, 2H, -CH ), 3.93 [t, 8H, -CH (hexyl)], 2.75 [m, 8H,
440 mg (2.8 mmol) 2,2’-bipyridyl and 2 g (2.33 mmol) N-(2,6-
diisopropylphenyl)-1,6-bis(4-tert-butylphenoxy)-9-bromopery-
lene-3,4-dicarboximide 13 were reacted as described for the
preparation of 14. Purification was carried out by column
chromatography on silica gel with CH Cl –toluene as eluent.
2
2
-CH (hexyl)], 1.1–1.6 [m, 26H, (CH ) (hexyl), -CH
2 3
(propyl)], 0.96 [m, 15H, CH (hexyl), CH (propyl)];
2
2
3
3
l
(CH Cl )/nm (e) (absorption) 277 (1.23), 414 (0.27), 538
(0.55); m/z (FD) 1132.8 (M+, 100%) (calc. M+, 1132.5).
max
2 2
2
2
Recrystallisation from CH Cl –methanol afforded 1.55 g of
2
2
the title compound as a red powder (86% yield).
N-Propyl-1,6,7,12-tetra(4-hexyloxyphenoxy)-9-bromoperylene-
3,4-dicarboximide 21
d (500 MHz, CDCl , 30 °C) 9.46 (d, 2H, H-7,7∞), 9.36 (d,
H
3
2H, H-12,12∞), 8.36 (s, 2H, H-5,5∞), 8.34 (s, 2H, H-2,2∞), 7.64
(d, 2H, H-8,8∞), 7.60 (d, 2H, H-10,10∞), 7.4–7.5 (m, 12H, H-
11,11∞, Ph-H-3,3∞,16,16∞), 7.29 (d, 4H, Ph-H-15,15∞), 7.09, 7.13
5 g (4.4 mmol) N-Propyl-1,6,7,12-tetra(4-hexyloxyphenoxy)-
perylene-3,4-dicarboximide 20 and 2 g (11 mmol) NBS were
dissolved in 600 mL of DMF. The reaction mixture was
reacted for 12 h at 60 °C. After cooling to room temperature,
the reaction mixture was poured into 3 L water–HCl (551).
The resulting precipitate was filtered, washed with water and
dried under vacuum. Precipitation from CH Cl into methanol
(d, 4H, Ph-H-2,2∞), 2.73 [m, 4H, CH(CH ) ], 1.34 (s, 36H,
3 2
tert-butyl) 1.15 [d, 24H, CH(CH ) ]; d (125.5 MHz, CDCl ,
3 2
C
3
30 °C) 163.2, 153.8, 153.7, 153.3, 147.3, 147.2, 145.7, 145.7,
140.1, 132.8, 131.9, 130.7, 129.7, 129.4, 128.9, 128.3, 127.9,
127.9, 127.2, 127.2, 127.0, 126.9, 124.3, 124.2, 123.9, 123.1,
2
2
121.6, 118.6, 118.5, 34.4, 31.5, 29.1, 24.0; n (KBr)/cm−1
afforded 4.68 g of the title compound 21 as a red powder
max
1709 (CNO), 1672 (CNO); l (CH Cl )/nm (e) 275 (66307),
93% yield).
max
2 2
417 (15681), 534 (91474); m/z (FD) 777.1 (M2+, 6%), 1554.1
d (500 MHz, CDCl , 30 °C) 8.12 (s, 1H, H-2), 8.10 (s, 1H,
H
3
(M+, 100%) [C
H
N O (1553.99 g mol−1) calc.: C, 83.47;
h-5), 8.09 (d, 1H, H-10), 7.38 (s, 1H, H-8), 7.18 (d, 1H, H-
108 100 2 8
H, 6.49; N, 1.80. Found: C, 83.31; H, 6.33; N, 1.62%]; mp
11), 6.7–7.0 (m, 16H, Ph-H), 4.05 (t, 2H, -CH ); 3.92 [t, 8H,
2
259 °C; R 0.84 (CH Cl ), 0.26 (toluene).
-CH (hexyl)]; 1.77 [m, 10H, -CH /-CH (hexyl)], 1.2–1.6 [m,
f
2 2
2
2
2
24H, (CH ) ], 0.94 [m, 15H, CH /CH (hexyl)]; m/z (FD)
2 3
3
3
1211.6 (M+, 100%) (calc. M+, 1211.4).
N,N∞-Bis(2,6-diisopropylphenyl)-1,6,11,16-tetra(4-tert-
butylphenoxy)quaterrylene-3,4513,14-bis(dicarboximide) 18
N,N∞-Dipropyl-1,1∞,6,6∞,7,7∞,12,12∞-octa(4-
hexyloxyphenoxy)-9,9∞-biperylene-3,453∞,4∞-bis(dicarboximide)
22
The synthesis was performed as described for 2. Modifications:
500 mg (0.32 mmol) N,N∞-bis(2,6-diisopropylphenyl)-1,1∞,6,6∞-
tetra(4-tert-butylphenoxy)-9,9∞-biperylene-3,453∞,4∞-bis(dicarb-
oximide) 17, 80 g KOH and 6 g glucose. The desired product
was purified by column chromatography on silica gel with
CH Cl –toluene as eluent. Precipitation from CH Cl into
654 mg (1 mmol) Bis(triphenylphoshine)nickel() chloride,
450 mg activated zinc and 131 mg (1 mmol) tetraethylam-
monium iodide were poured into a 100 mL Schlenk flask under
2
2
2 2
2368
J. Mater. Chem., 1998, 8(11), 2357–2369

6
7
8
9
M. Burghard, C. Fischer, M. Schmelzer, S. Roth, M. Hanack and
argon containing 80 mL of THF. After stirring for 4 h at room
temperature, 1.2 g (1.06 mmol) N-propyl-1,6,7,12-tetra(4-hex-
yloxyphenoxy)-9-bromoperylene-3,4-dicarboximide 21 were
added. Then, the reaction mixture was stirred for 12 h at room
W. Gopel, Chem. Mater., 1995, 7, 2104.
¨
D. Schlettwein, D. Wohrle, E. Karmann and U. Melville, Chem.
¨
Mater., 1994, 6, 3.
H. O. Loutfy, A. M. Hor, P. Kazmaier and M. Tam, J. Imaging
Sci., 1989, 33, 151.
M.P. O’Neil, M. P. Niemczyk, W. A. Svec, D. Gosztola, G. L.
Gaines III and M. R. Wasielewski, Science, 1992, 257, 63.
temperature. The reaction mixture was filtered through Al O
2 3
and washed with CH Cl . Precipitation from CH Cl into
2
2
2 2
methanol afforded 3.45 g of the title compound as a red
powder (75% yield). The purity was sufficient for the next
reactions. For analytical purposes, 100 mg were purified by
column chromatography on silica gel with toluene as eluent.
d (300 MHz, CDCl , 30 °C) 8.11 (s, 2H, H-2,2∞), 8.09 (s,
2H, H-5,5∞), 7.42 (d, 2H, H-10,10∞), 7.1–7.2 (m, 20H, Ph-H-
3,3∞,3◊,3◊, H-8,8∞,11,11∞), 6.7–6.9 (m, 16H, Ph-H-2,2∞,2◊,2◊∞),
4.05 (t, 4H, N-CH -), 1.68 (t, 4H, -CH -CH -CH ), 1.26 (3s,
72H, tert-butyl), 0.93 (t, 24H, CH ); m/z (FD) 1909.2 (M+,
d (300 MHz, CDCl , 30 °C) 8.12 (s, 2H, H-2,2∞), 8.11 (s,
2H, H-5,5∞), 7.42 (d, 2H, H-10,10∞), 7.08 (s, 2H, H-8,8∞),
6.7–7.0 (m, 34H, H-11,11∞,Ph-H-2,2∞,2◊,2◊∞,Ph-H-3,3∞,3Á,3◊∞),
10 R. Gvishi, R. Reisfeld and Z. Bursheim, Chem. Phys. Lett., 1993,
213, 338.
11 G. Seybold and G. Wagenblast, Dyes Pigm., 1989, 11, 303.
12 E. Clar, W. Kelly and R. M. Laird, Monatsh. Chem., 1956, 87, 391.
13 E. Clar and J. C. Speakman, J. Chem. Soc., 1958, 2492.
H
3
14 (a) K.-H. Koch and K. Mullen, Chem. Ber., 1991, 124, 2091;
¨
A. Bonhen, K.-H. Koch, W. Luttke and K. Mullen, Angew.
¨
¨
Chem., Int. Ed. Engl., 1990, 29, 525; (b) S. De Backer, M. R.
Negri, S. De Feyter, G. B. Dutt, M. Ameloot, F. C. De Schryver,
2
2
2
3
K. Mullen and F. Holtrup, Chem. Phys. Lett., 1995, 233, 538;
¨
3
A. Schmidt, N. R. Armstrong, C. Goeltner and K. Mullen,
¨
100%), 955 (M2+, 92%) (calc. M+, 1910.4).
J. Phys. Chem., 1994, 98, 11780; S. De Backer, G. B. Dutt, M.
H
3
Ameloot, F. C. De Schryver, K. Mullen and F. Holtrup, J. Phys.
¨
Chem., 1996, 100, 512; Y. H. Meyer, P. Plaza and K. Mullen,
¨
Chem. Phys. Lett., 1997, 264, 643.
4.06 (t, 4H, -CH2), 3.93 [t, 16H, -CH (hexyl)], 1.76 [m,
15 F. Holtrup, G. R. Muller, H. Quante, S. De Feyter, F. C. De
¨
2
20H, -CH /-CH (hexyl)], 1.3–1.7 [m, 48H, (CH ) ], 0.93 [m,
Schryver and K. Mullen, Chem. Eur. J., 1997, 3, 219.
¨
2
2
2 3
16 H. Quante, Y. Geerts and K. Mullen, Chem. Mater., 1997, 9, 495.
17 H. Quante and K. Mullen, Angew. Chem., Int. Ed. Engl., 1995, 34,
¨
30H, CH /CH (hexyl)]; m/z (FD) 1131.6 (M2+, 100%),
3
3
¨
2263.1 (M+, 62%) (calc. M+, 2262.9).
1323; H. Quante, Ph.D. Dissertation, Mainz, 1995.
18 Y. Nagao and T. Misono, Bull. Chem. Soc. Jpn., 1981, 54, 1191.
19 Y. Nagao, Y. Abe and T. Misono, Dyes Pigm., 1991, 16, 19.
20 T. Yamamoto, A. Morita, Y. Miyazaki, Y. Maruyama,
H. Wakayama, Z. Zhou, Y. Nakamura and T. Kanbara,
Macromolecules, 1992, 25, 1214.
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1981, 215, 49.
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Ed. Engl., 1986, 25, 508; (b) I. P. Beletskaya, J. Organomet. Chem.,
1983, 250, 551.
N,N∞-Dipropyl-1,6,7,10,11,16,17,20-octa(4-
hexyloxyphenoxy)quaterrylenebis(dicarboximide) 23
500 mg (0.22 mmol) N,N∞-dipropyl-1,1∞,6,6∞,7,7∞,12,12∞-octa(4-
hexyloxyphenoxy)-9,9∞-biperylene-3,453∞,4∞-bis(dicarboximide)
22, 30 g KOH and 4 g glucose, dissolved in 30 mL of ethanol,
were reacted as described for the preparation of 2. Purification
was carried out by column chromatography on silica gel with
CH Cl as eluent. Recrystallisation from CH Cl –methanol
23 Ullmanns Enzyclopa¨die der technischen Chemie, 4th edn., Verlag
Chemie, Weinheim, 1974, vol. 18, p. 686.
24 W. Bradly and F. W. Pexton, J. Chem. Soc., 1954, 4432.
25 D. Dotcheva, M. Klapper and K. Mullen, Macromol. Chem.
2
2
2 2
afforded 119 mg of a green powder containing the title com-
pound and some degradation products, i.e. loss of hexyloxy-
phenoxy side groups. The title compound was finally purified
by gel permeation chromatography in chloroform on poly-
styrene as stationary phase, affording 15 mg (0.3% yield).
d (500 MHz, CDCl , 30 °C) 8.08 (s, 4H, H-2,5,12,15), 8.06
¨
Phys., 1994, 195, 1905; H. Quante, P. Schlichting, U. Rohr, Y.
Geerts and K. Mullen, Macromol. Chem. Phys., 1996, 197, 4029.
¨
26 R. H. Mitchell, Y.-H. Lai and R. V. Williams, J. Org. Chem.,
1979, 44, 4733.
27 I. T. Storie and F. Sontheimer, Tetrahedron Lett., 1978, 19, 4567.
28 (a) M. Iyoda, M. Sakaitami, H. Otsuka and M. Oda, Chem. Lett.,
1985, 127; (b) M. Iyoda, M. Sakaitami, A. Kojima and M. Oda,
Tetrahedron Lett., 1985, 26, 3719.
29 A. S. Kende, L. S. Liebeskind and D. Braitsch, Tetrahedron Lett.,
1975, 16, 3375.
30 S. Prathapan, T. E. Johnson and J. Lindsey, J. Am. Chem. Soc.,
1993, 115, 7519.
31 M. Emmelius, G. Pawlowski and H. W. Vollmann, Angew. Chem.,
1989, 101, 1475.
32 (a) G. Scheibe, Angew. Chem., 1937, 50, 51; (b) G. Scheibe, Kolloid
Zeitsch., 1938, 82, 1; (c) E. E. Jelley, Nature, 1936, 138, 1009; (d)
E. E. Jelley, Nature, 1937, 139, 631; (e) S. F. Mason, Proc. Chem.
H
3
(s, 4H, H-8, 9, 18, 19), 6.93 (d, 4H, Ph-H-3,3∞), 6.92 (d, 4H,
Ph-H-3◊,3◊∞), 6.84 (d, 4H, Ph-H-2,2∞), 6.82 (d, 4H, Ph-H-
2◊,2◊∞), 4.04 [t, 4H, -CH (propyl)], 3.94 [m, 8H, -CH (Ph)],
2
2
1.77 [m, 8H, -CH (Ph)], 1.68 [m, 4H, -CH (propyl)], 1.47
2
2
[m, 8H, -CH (Ph)], 1.37 [m, 16H, (CH ) (Ph)], 0.93 [m, 18H,
2 2
CH (Ph), CH (propyl)]; l (CH Cl )/nm (e) 258 (1.27),
2
2
2
max
2 2
271 (1.28), 790 (1.45); m/z (FD) 2260.7 (M+, 100%), 2066.8
([M−Ph]+, 54%), 1874.8 ([M−2Ph]+, 66%), 1681.6
(M−3Ph]+, 49%), (calc. M+, 2261.1).
Soc., 1964, 119; ( f ) D. Mobius, Adv. Mater., 1995, 7, 437.
¨
33 K. A. Connors, Binding Constants, Wiley, New York, 1987.
34 Y. Geerts and K. Mullen, Novel Light Emitting Dyes, Oligomers,
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¨
115, 2927.
5
H. Langhals, Heterocycles, 1995, 40, 477.
Paper 8/04337J
J. Mater. Chem., 1998, 8(11), 2357–2369
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