Novel perylene chromophores obtained by a facile oxidative cyclodehydrogenation route

Article abstract of DOI:10.1002/1521-3765(20010518)7:10<2197::AID-CHEM2197>3.0.CO;2-G

New perylene chromophores, phenyl-substituted diindeno[1,2,3-cd: 1′,2′,3′-lm]perylenes 5a,b and 4,4′,7,7′-tetraphenyldiacenaphtho[1,2- k:1′,2′,k′]diindeno[1,2,3-cd:1′,2′,3′- me]perylenes 22a,b, have been synthesized from substituted fluoranthene derivatives 3 a,b and 4 a,b by means of a surprisingly simple oxidative cyclodehydrogenation reaction. The resulting chromophores, when substituted with alkyl chains at the periphery, show good solubility in organic solvents, and a full characterization of the novel red, green, and blue dyes by field-desorption mass spectrometry, UV/Vis and ¹H and ¹³C NMR spectroscopy becomes possible.

Full text of DOI:10.1002/1521-3765(20010518)7:10<2197::AID-CHEM2197>3.0.CO;2-G

FULL PAPER
Novel Perylene Chromophores Obtained by a Facile Oxidative
Cyclodehydrogenation Route
Mike Wehmeier, Manfred Wagner, and Klaus Müllen*[a]
Abstract: New perylene chromophores, phenyl-substituted diindeno[1,2,3-cd:
1',2',3'-lm]perylenes 5a,b and 4,4',7,7'-tetraphenyldiacenaphtho[1,2-k:1',2',k']di-
indeno[1,2,3-cd:1',2',3'-me]perylenes 22a,b, have been synthesized from substituted
fluoranthene derivatives 3a,b and 4a,b by means of a surprisingly simple oxidative
cyclodehydrogenation reaction. The resulting chromophores, when substituted with
alkyl chains at the periphery, show good solubility in organic solvents, and a full
characterization of the novel red, green, and blue dyes by field-desorption mass
spectrometry, UV/Vis and 1H and 13C NMR spectroscopy becomes possible.
Keywords: chromophores ´
dehydrogenation ´ dyes/pigments
well as their alkyl-substituted derivatives 3b and 4b. Molec-
ular orbital calculations[12] suggest that radical cations of 3 and
4 possess the highest spin density mainly on the peri-positions.
We therefore assumed that oxidation of 3 and 4 to the
Introduction
Since the discovery of fullerenes, polycyclic aromatic hydro-
carbons (PAHs) have regained considerable interest. From a
synthetic point of view, it is challenging to create
fullerene subunits[1, 2] and to produce larger and
more complex PAHs.[3±5] Furthermore, investiga-
tions are stimulated by the useful properties of
PAHs in optoelectronics[6] and dyestuff chemis-
try.[7] Recently, our group established a two-step
method to extended polycyclic aromatic hydro-
carbons such as 1 and 2. The synthetic approach
for 1 and 2 involves the construction of soluble
polyphenylene precursors with a close spatial
arrangement of the phenyl rings followed by a
planarization of these precursors to the PAHs by
intramolecular cyclodehydrogenation.[8±10] Com-
pounds such as 1 and 2 are building blocks for
supramolecular architectures, for example,
1
shows a stable discotic mesophase over a wide
temperature range and forms monomolecular
adsorbate layers on suitable substrates.[8, 11]
In this paper, we report the extension of the
aforementioned dehydrogenative coupling route
to PAHs with five-membered rings, namely
7,8,9,10-tetraphenylfluoranthene (3a) and 7,14-
diphenylacenaphtho[1,2-k]-fluoranthene (4a) as
[a] Prof. Dr. K. Müllen, Dr. M. Wehmeier,
Dr. M. Wagner
Max-Planck-Institut für Polymerforschung
Ackermannweg 10, 55128 Mainz (Germany)
Fax : (‡49)6131-379-350
E-mail: muellen@mpip-mainz.mpg.de
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K. Müllen et al.
FULL PAPER
corresponding radical cations could allow not only intra-
molecular cyclodehydrogenation, but also intermolecular
oxidative coupling, which leads to more complex molecular
structures such as the perylene chromophores 5a and 5b.
Perylenes are important chromophores in dye-stuff chemis-
try[13±15] due to their excellent thermal, chemical, and photo-
chemical stability and they have recently been applied in
photovoltaic cells[16] and optical switches.[17]
synthesis of a 7,8,9,10-tetrakis(4-dodecylphenyl)fluoranthene
(3b) required a new tetra-phenylcyclopentadienone deriva-
tive 9b. This should then be subjected to Diels ± Alder
cycloaddition with acenaphthylene (10) in a similar fashion
to the parent, commercially available tetraphenylcyclopenta-
dienone 9a (see Scheme 1).
Our group has synthesized terrylene (7) and quaterrylene
(8) dyes, which constitute homologues of the well-known
perylenetetracarboxdiimides (6).[18±20] The key steps of their
synthesis consist of a palladium-catalyzed coupling reaction of
suitable precursors followed by a final bond closure to the
double-stranded rylene structure. The proposed cyclodehy-
drogenation route further extends the class of perylene
chromophores.
Results and Discussion
Synthesis: Alkyl substitution is a prerequisite for the solubi-
lization of large polycyclic aromatic hydrocarbons and is also
important for the formation of liquid crystalline phases. The
Scheme 1. Synthetic pathway to 2,3,4,5-tetrakis(4-dodecylphenyl)-cyclo-
pentadien-1-one (9b) with R ˆ (CH2)11CH3.
The tetradodecyl-substituted derivative 9b had to be syn-
thesized in a twofold aldol condensation reaction of diben-
zylketone 13 and diketone 17; this is a variation of the
reaction conditions published by Grummit and Johnson.[21]
Alkyl-substituted dibenzylketone 13 was available in a two-
step procedure: bromomethylation of dodecylbenzene (11)
with sodium bromide and para-formaldehyde in a mixture of
concentrated sulfuric acid and glacial acetic acid yielded
4-bromomethyl dodecylbenzene (12). The raw product con-
tained a mixture of ortho- and para-isomers, and after work-
up the desired compound 12 could be isolated in 20% yield
only. Afterwards, 12 was converted into the desired com-
pound 13 by a carbonylation reaction with iron pentacarbonyl
under phase-transfer conditions following the reports of
Otsuji[22] and Thilmont (yield: 67%).[23] The synthesis of the
alkyl-substituted diketone 17 was accomplished by using a
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Novel Perylene Chromophores
2197±2205
procedure of Mueller-Westerhoff,[24] which includes lithiation
of 4-bromododecylbenzene (16) with sec-butyllithium in
tetrahydrofuran and subsequent treatment with 1,4-dimethyl-
piperazine-2,3-dione (yield of 17: 50%). The aforementioned
4-bromododecylbenzene (16) was readily available by Frie-
del ± Crafts acylation of bromobenzene (14) with lauroyl
chloride (yield: 53%) followed by a Wolff ± Kishner reduction
of the resulting ketone 15 (yield: 76%). The Diels ± Alder
reaction of 9a,b with 10 gave a mixture of 3a,b and the
dihydroderivative 3'a,b. Subsequent treatment of this mixture
with KMnO4 in refluxing acetone provided 3a,b in essentially
quantitative yield.
anthene derivatives. Therefore, it was necessary to modify
the conditions as reported elsewhere for derivatives of 1.[20]
Successful intermolecular coupling of 3a and b in almost
quantitative yield was achieved by adding a solution of FeCl3
in nitromethane, rather than solid FeCl3, to a solution of the
precursors in dichloromethane, while strongly purging with
argon. Predissolving the oxidizing agent in nitromethane
speeds up the desired reaction, while bubbling with argon
helps to remove evolving HCl, which otherwise facilitates
undesired chlorination of the aromatic reactant. Surprisingly,
the coupling reaction of tetraphenylfluoranthene 3a and the
alkyl-substituted homologue 3b using the above-described
method afforded different structural motifs (Scheme 2).
While in the case of 3a only intermolecular coupling to the
red chromophore 5a occurred, the intermolecular coupling of
3b was accompanied by an intramolecular reaction of the
peripheral phenyl rings that leads to the dark green colored
compound 5b with an extended polyaromatic system. The
synthetic results are independent of the amount of oxidizing
agent.
The key step of the synthetic route was the oxidative
coupling reaction of the tetraphenylfluoranthene precursors
3a,b. In the literature, various reaction systems like AlCl3/
NaCl (Scholl reaction),[25] Tl(OCOCF3)3,[26] CoF3/TFA,[27]
[29]
SbCl5,[28] or FeCl3 are reported for such oxidative cyclo-
dehydrogenation reactions. Recently, Bard[30] synthesized
dibenzotetraphenylperiflanthene (19) in moderate (56%)
The almost quantitative yields of the above-described
syntheses gave hope that treatment of 4a,b under the same
conditions would allow a polymerization that leads to the
ladder-type structures 26a,b. The synthetic pathway to 4a,b is
outlined in Scheme 3.
The synthetic buildup of both precursors (4a,b) proceeded
analoguous to compounds 3a,b by a method originally
developed by Dilthey.[31] After a twofold aldol condensation
of the dibenzyl ketones 13a,b and acenaphthenequinone 20
yield by treatment of (7,12-diphenyl)-
benzo[k]fluoranthene (18) with CoF3
in trifluoroacetic acid.
Applying this method to 3a, we
found
that
conversion
into
4,4',5,5',6,6',7,7'-tetraphenyldiindeno-
[1,2,3-cd:1',2',3'-lm]perylene (5a) was
low, and large amounts of the starting
material were recovered. We then
changed to experimental procedures
established in our group for the syn-
thesis of large polycyclic aromatic
hydrocarbons: successful cyclodehy-
drogenation reactions have been per-
formed under Kovacic conditions
(AlCl3/Cu triflate/CS2)[8] or FeCl3 in
dichloromethane.[10] However, ex-
periments on 3a,b under these reac-
tion conditions led to undesired mul-
tifold chlorination of the fluor-
Scheme 2. Synthetic pathway to 5a and 5b with a: R ˆ H and b: R ˆ (CH2)11CH3. i) DT, reflux xylene;
ii) KMnO4; iii) FeCl3/CH3NO2; iv) FeCl3/CH3NO2.
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K. Müllen et al.
FULL PAPER
spectroscopic data only for 5a
and 22b. Planarization of the
outer phenyl rings from 3b to
5b becomes apparent in the
1H NMR spectra. In accordance
with the extended p-system,
resonances occur at consider-
ably lower field than for the
non-planarized analogue 5a.
The assignment, based on two-
dimensional
H,H-correlated
NMR analysis of the resonan-
ces, is given in Table 1.
As was mentioned before,
compound 5b was expected to
be a candidate for thermotropic
liquid crystalline phase behav-
ior. However, when 5b was
investigated by means of polar-
ization microscopy, differential
scanning calorimetry, and X-ray
diffractrometry, no transition
into a discotic mesophase could
be observed. By means of a
polarization microscope, a di-
rect transition of the crystalline
solid into the isotropic melt was
visible above 3008C under a
nitrogen atmosphere.
Electronic spectra: The three
perylene chromophores form
deep red (5a), green (5b), and
blue (22a,b) solutions in com-
mon organic solvents like
Scheme 3. Synthetic pathway to 7,14-diphenylacenaphtho[1,2-k]-fluoranthenes (4a,b) and oxidative cyclodehy-
drogenation of 4a,b to 22a,b with a: R ˆ H and b: R ˆ (CH2)11CH3 i) KOH/EtOH, DT; ii) acenaphthylene (10),
DT; iii) FeCl3/CH3NO2.
(yield: 86 ± 94%), the resulting 7,9-diphenyl-8H-cyclopenta-
[1]acenaphthylen-8-ones (21a,b) were treated with acenaph-
thylene (16) in a [4‡2]-cycloaddition followed by treatment
with KMnO4 in acetone to give the desired 7,14-diphenylace-
naphtho[1,2-k]-fluoranthenes (4a,b) (yield: 83 ± 87%). Com-
pounds 4a,b were then subjected to oxidative cyclodehydro-
genation under the same reaction conditions as for 3a,b with
the aim of constructing an extended ladder-type polymer by
means of oxidative coupling at both ends of the molecule.
However, work-up of the reaction led exclusively and
quantitatively to a blue reaction product that could be
unambiguously characterized as 4,4',7,7'-tetraphenyldiace-
naphtho[1,2-k:1',2',k']diindeno-[1,2,3-cd:1',2',3'-me]perylenes
(22a,b).
Table 1. Aromatic 1H NMR chemical shifts of 5a, 5b, 22a, and 22b in
C2D2Cl4 at 1358C.
d
Type
H
Integration
5a
5b
7.8
d
1
4H
10H
10H
4H
4H
4H
4H
4H
4H
4H
4H
4H
24H
4H
4H
4H
4H
4H
8H
8H
4H
4H
4H
7.30 ± 7.26
6.87 ± 6.78
6.55
9.42
8.87
8.84
8.76
8.68
8.08
7.65
7.83
7.75 ± 7.71
7.3
6.72
6.64
7.83
7.66
7.58
m
m
d
d
s
d
s
s
d
d
d
m
dd
d
d
d
d
d
H phenyl
H phenyl
2
3
7
1
6
5
2
4
1
22a
22b
3,4,5,8
7
6
2
1
8
3 or 4
3 or 4
7
6
2
All attempts to obtain higher oligomers under harsher
reaction conditions (e.g. use of SbCl5 as oxidizing agent),
higher reaction temperatures, and longer reaction times
failed.[32]
Structure elucidation: The structures of 5a, 5b, 22a, and 22b
were proven by 1H NMR spectroscopy, field-desorption mass
spectrometry, and UV/Vis spectroscopy. As a result of
solubility problems, it was possible to obtain 13C NMR
7.51
7.29
6.81
6.64
d
dd
d
d
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Novel Perylene Chromophores
2197±2205
phenyl rings and the resulting
extension of the aromatic p-
system, not only a bathochro-
mic shift becomes apparent, but
also the absorption coefficient
increases. All solutions are
highly fluorescent, with a bright
fluorescence under UV irradi-
ation and even a pronounced
fluorescence under ambient
lighting. Figure 2 shows the cor-
responding UV/Vis absorption
and fluorescence spectra mea-
sured in chloroform for 5a.
The Stokes shift is small,
which can be explained by the
rigid structure of the chromo-
phoric unit. Table 2 summarizes
Figure 1. UV/Vis spectra of 5a (solid line) and 5b (dotted line) in chloroform.
UV/Vis spectroscopic data of
the precursor molecules 3 and 4, chromophores 5a, 5b, 22,
parent periflanthene (23),[33] dibenzotetraphenyl-periflan-
thene 19 synthesized by Bard,[30] and a model compound 24
for a ladder polymer of similar structural type reported by
chloroform or toluene. As can be seen from Figure 1 and
Figure 2, absorption of the three chromophores covers a
broad range of the visible spectrum. Comparison of 5a and 5b
shows that, in accordance with the planarization of the outer
Figure 2. A: UV/Vis absorption (dotted line) and fluorescence (solid line) spectra of 5a in chloroform. For e values of compound 5a see Figure 1; B: UV/Vis
absorption (dotted line) and fluorescence (solid line) spectra of 5b in chloroform. For e values of compound 5b see Figure 1; C: UV/Vis absorption (dotted
line) and fluorescence (solid line) spectra of 22a in chloroform. Due to the low solubility of compound 22a (a: R ˆ H), the e values could not be determined;
D: UV/Vis absorption (dotted line) and fluorescence (solid line) spectra of 22b (b: R ˆ (CH2)11CH3) in chloroform. For e values of compound 22b, see
Experimental Section.
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K. Müllen et al.
FULL PAPER
Schlüter[34] as well as the rylenetetracarboximides
synthesized in our group recently.
Table 2. Summarized UV data (lmax, log e, and lmax of fluorescence) of compounds 3, 4,
5a, 5b, 6, 7, 19, 22, 23, and 24.
lmax
log e
maximum of
Clearly visible is the strong bathochromic shift of
roughly 150 nm as a result of the dimerization and
the corresponding buildup of a perylene chromo-
phoric subunit of 3 to 5 and 4 to 22, respectively.
Comparing the absorption maxima of the parent
polyaromatic unit periflanthene (23) with that of
octaphenylperiflanthene (5a), one observes that
only a small bathochromic shift of 25 nm is obtained
by attaching eight phenyl rings. The small shift is
based on the fact that the outer phenyl rings rotate
out of the plane of the aromatic p-system. In
contrast, twofold acenaphthoannelation like for
compound 22b or planarization into compound 5b
leads to a strong bathochromic shift due to the
extension of the p-system. Compound 24 illustrates
that not only simple extension of the p-system is a
prerequisite for absorbance at low energies. The
ladder structure 24 is by far more extended than
those of 22 and 19, but as a result of their perylene
subunit, compound 19 absorbs at a comparable
wavelength and 22 even at lower energies. When
the spectroscopic data of 5a, 5b, and 22b are
compared with the rylene structures 6, 7, and 8, the
chromophores presented in this paper can be
considered attractive candidates for fluorescent
materials. With regard to the ease of the synthetic
buildup in relatively few steps from commercially
available starting compounds and the absorption
maxima between perylene and the terrylenediimide,
this holds specially true for the red chromophore
(5a) and blue chromophore 22. In contrast, for the
synthesis of the green chromophore 5b, a multistep
procedure has to be undertaken. However, with the
absorption maxima at lower energies than 7 and
only a few known fluorophores absorbing in this
region of the visible spectrum, 5b can also be
expected to be an attractive dye.
1
[nm]
[Lmol 1 cm
]
fluorescence[a] [nm]
[b]
375
4.4
[b]
427
4.41
[b]
540
564
3.79
4.94
587
670
4.99
696
602
5.06
632
Conclusion
[b]
[b]
581
582
We present the synthesis of perylene derivatives 5a,
5b, and 22 by means of a short and convenient
synthetic scheme. They show intense absorptions in
the range from 550 nm (5a) to 670 nm (5b) and,
remarkably, strong emissions from 590 nm (5a) to
700 nm (5b). The ease of the synthetic buildup
should make it possible to incorporate functional
groups by the buildup of the corresponding tetra-
phenylcyclopentadienones. Hereby, tailor-made
spectroscopic properties could be achieved, which
are a prerequisite for applications that require dyes
with absorption and emission in a specific region of
the visible spectrum. The same synthetic strategy
could be used to covalently link the dyes to
polymers and therefore obtain migration-stable
immobilized dyes. For a more comprehensive as-
[b]
[b]
525
664
4.67
5.08
556
707
[a] Excitation in the maximum of absorption. [b] Not available.
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Novel Perylene Chromophores
2197±2205
1
ˆ
ˆ
23.1, 14.5; nÄ ˆ 1711 (C O), 1672 cm (C O); MS (FD): m/z (%): 338.5
sessment of the potential of the synthesized chromophores, a
detailed investigation of the photophysical properties is
ongoing.
‡
([M] , 100).
4-Bromododecylbenzene (16): A mixture of 4-bromododecanoylbenzene
(15) (200 g, 589 mmol), hydrazine hydrate (98%, 85.8 mL), and KOH
(132 g, 2.36 mol) in triethylene glycol (1 L) was refluxed for 2 h. The
mixture was deionized at atmospheric pressure until the temperature of the
reaction mixture reached 2108C. After cooling to room temperature, the
resulting mixture was poured into water, acidified with conc. HCl solution
(220 mL), and extracted with dichloromethane. The organic phase was
washed with water, dried with magnesium sulfate, and concentrated under
reduced pressure. The residue was purified by column chromatography on
silica gel with petroleum ether to afford the benzene 16 as a colorless oil
(yield 68%).
Experimental Section
Spectral data were obtained on NicoletFT-IR 320 (IR), Perkin Elmer-
Lambda 9 and 15 (UV/Vis), Varian Gemini 200, BrukerAC 300, or
AMX 500 (NMR). For the 2D-1H-1H NMR experiment, the cosy45
pulseprogram was used with a 90 degree pulse of 16 us and a relaxation
delayd1 of 4 s.
1H NMR (300 MHz, CDCl3, 308C): d ˆ 7.40 (d, J ˆ 8.0 Hz, 2H), 7.06 (d, J ˆ
8.0 Hz, 2H), 2.58 (t, J ˆ 7.5 Hz, 2H), 1.61 (p, J ˆ 7.5 Hz, 2H), 1.36 ± 1.18 (m,
18H), 0.92 (t, J ˆ 7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3, 308C): d ˆ
142.25, 131.65, 130.56, 119.64, 35.76, 32.33, 31.72, 30.05, 29.98, 29.87,
FinniganMAT 312 (FD-MS) instruments were used. The melting points
(m.p.) have been reported uncorrected. FeCl3 was purchased from Merck,
and all other chemicals were purchased from Aldrich and used as received.
Tetrahydrofuran was deionized before use. All other solvents were used as
received. KOH/EtOH was prepared by dissolving KOH (3 g) in ethanol
(15 mL) at elevated temperature.
‡
29.76, 29.60, 23.10, 14.51; MS (FD): m/z (%): 324.2 ([M] , 100).
4,4'-Didodecylbenzil (17): sec-Butyllithium (0.11 mol) was added to
4-bromododecylbenzene (16) (35.8 g, 0.11 mol) in tetrahydrofuran
(100 mL) at 788C. The reaction mixture was allowed to warm to 08C
and subsequently added to a suspension of 1,4-dimethylpiperazine-2,3-
dione (7.1 g, 0.05 mol) in tetrahydrofuran (180 mL). After stirring over-
night, the reaction was quenched with HCl (300 mL, 2n). Dichloromethane
(300 mL) was then added, and the organic phase was separated, washed
with HCl (2n) and deionized water, and dried over magnesium sulfate. The
solvent was evaporated under vacuum. The resulting solid was purified by
chromatography on silica gel with a mixture of dichloromethane and
petroleum ether (3:1) as eluent (yield 57%).
4-Bromomethyldodecylbenzene (12): Semi-concentrated sulfuric acid
(80 mL) was added to a mixture of dodecylbenzene (75 g, 303 mmol),
para-formaldehyde (12.5 g, 420 mmol), sodium bromide (51.6 g), and
glacial acetic acid (24 mL) over 3 h. The reaction mixture was then stirred
for another 12 h at the same temperature. After cooling to room temper-
ature, deionized water (300 mL) was added. The reaction mixture was
extracted with dichloromethane, the organic phase was separated, dried
over magnesium sulfate, and the solvent was evaporated under vacuum.
The resulting precipitate was purified by chromatography on silica gel with
petroleum ether as eluent (24% yield).
M.p. 478C. 1H NMR (300 MHz, CDCl3, 308C): d ˆ 7.90 (d, J ˆ 8.2 Hz, 4H),
7.30 (d, J ˆ 8.2 Hz, 4H), 2.68 (t, J ˆ 7.4 Hz, 4H), 1.8 ± 1.1 (m, 40H), 0.88 (d,
J ˆ 7.6 Hz, 6H); 13C NMR (75 MHz, CDCl3, 308C): d ˆ 194.8, 151.2, 131.2,
128.8, 129.3, 36.5, 32.2, 31.3, 29.9, 29.8, 29.7, 29.6, 29.5, 23.0, 14.4; nÄ ˆ
M.p. 468C. 1H NMR (300 MHz, CDCl3, 308C): d ˆ 7.32 (d, 3J(H,H) ˆ
8.2 Hz, 2H; Ar H), 7.17 (d, 3J(H,H) ˆ 8.2 Hz, 2H; Ar H), 4.51 (s, 2H;
H-5), 2.62 (t, 3J(H,H) ˆ 7.6 Hz, 4H; a-CH2 ), 1.70 ± 1.20 (m, 20H; CH2 ),
3
0.91 (t, J(H,H) ˆ 6.5 Hz, 3H; CH3); 13C NMR (75 MHz, CDCl3, 308C):
1
‡
ˆ
1671 cm (C O); MS (FD): m/z (%): 546.3 ([M] , 100); elemental
analysis calcd (%) for C38H58O2 (546.87): C 83.46, H 10.69; found C 83.49, H
10.89.
d ˆ 143.9, 135.4, 129.4, 129.2, 36.4, 36.1, 34.2, 32.3, 31.7, 30.1, 30.0, 29.9, 29.8,
‡
29.7, 23.1, 14.5; MS (FD): m/z (%): 340.5 ([M] , 100); elemental analysis
calcd (%) for C19H31Br (339.35): C 67.25, H 9.20, Br 23.54; found C 67.16, H
9.26, Br 23.31.
Tetra(4-dodecyl-phen-1-yl)cyclopentadienone (9b): A solution of KOH
(1.2 g, 22 mol) in ethanol (6 mL) was added to a refluxing solution of 4,4'-
didodecylbenzil (17) (12 g, 22 mmol) and 1,3-bis(4-dodecylphenyl)-propan-
2-one (13) (10.81 g, 20 mmol) in ethanol (36 mL). After five minutes the
reaction was cooled to 08C, and the resulting purple oil was separated from
the solvent. Column chromatography of this viscous oil eluted with
petroleum ether/CH2Cl2 (4:1) as eluent afforded 9b as a purple solid (yield
43%).
1,3-Bis(4-dodecylphenyl)-propan-2-one (13b): Iron pentacarbonyl (7.3 g,
4.9 mL, 37 mmol) was added to a refluxing mixture of 4-bromomethyldo-
decylbenzene (24 g, 71 mmol) (12), sodium hydroxide (12.3 g), benzyltri-
ethylammonium chloride (0.54 g), deionized water (7 mL), and dichloro-
methane (170 mL) under a nitrogen atmosphere. The reaction mixture was
then refluxed with rigorous stirring overnight. After cooling to room
temperature, the reaction mixture was neutralized with HCl (2n), the
organic phase was separated, washed with HCl (2n) and deionized water,
dried over magnesium sulfate, and the solvent was evaporated under
vacuum. The resulting solid was purified by chromatography on silica gel
with a mixture of dichloromethane and petroleum ether (3:1) as eluent
(47% yield).
M.p. 558C. 1H NMR (300 MHz, CDCl3, 308C): d ˆ 7.19 (d, J ˆ 8.2 Hz, 4H),
7.05 (d, J ˆ 8.2 Hz, 4H), 6.98 (d, J ˆ 8.2 Hz, 4H), 6.83 (d, J ˆ 8.2 Hz, 4H),
2.55 (t, J ˆ 7.5 Hz, 4H), 1.8 ± 1.1 (m, 40H), 0.91 (d, J ˆ 7.6 Hz, 6H);
13C NMR (75 MHz, CDCl3, 308C): d ˆ 154.6, 143.6, 142.5, 131.2, 130.4,
129.8, 128.9, 128.5, 128.3, 125.2, 36.2, 32.4, 31.7, 31.5, 30.2, 30.0, 29.9, 29.7,
1
‡
1
3
ˆ
23.2, 14.6; nÄ ˆ 1710 cm (C O); MS (FD): m/z (%): 1057.0 ([M] , 100);
elemental analysis calcd (%) for C77H116O (1108.16): C 87.43, H 11.05;
found C 87.12, H 11.02.
M.p. 72 ± 748C. H NMR (300 MHz, CDCl3, 308C): d ˆ 7.15 (d, J(H,H) ˆ
8.0 Hz, 4H; Ar H), 7.07 (d, 3J(H,H) ˆ 8.0 Hz, 4H; Ar H), 3.69 (s, 4H;
H-2), 2.60 (t, 3J(H,H) ˆ 7.4 Hz, 4H; a-CH2 ), 1.70 ± 1.10 (m, 40H; CH2 ),
0.91 (t, J(H,H) ˆ 6.8 Hz, 6H; CH3); 13C NMR (75 MHz, CDCl3, 308C):
3
7,8,9,10-Tetraphenylfluoranthene (3a): A mixture of acenaphthylene (10)
(1.9 g, 12.5 mmol) and tetraphenylcyclopentadienone (9a) (5.11 g,
13.3 mmol) in xylene (40 mL) was refluxed for 16 h under an argon
atmosphere. After cooling to room temperature, ethanol (300 mL) was
added to the reaction mixture. The precipitated solid was filtered, washed
with ethanol, and dried in vacuum. Subsequently, the solid was dissolved in
a refluxing mixture of acetone/benzene (1:5, 100 mL) and treated with
aliquots of a solution of KMnO4 in acetone until the reaction mixture
remained purple. After filtration over a column of silica gel to remove
KMnO4, evaporation of the solvent, and drying in vacuum, 3a was obtained
as a yellow, strongly fluorescent solid (yield 85%).
d ˆ 206.5, 142.2, 131.7, 129.8, 129.2, 49.2, 36.1, 32.4, 31.9, 30.0, 29.8, 23.2,
1
‡
ˆ
ˆ
14.6; nÄ ˆ 1715 (C O), 1677 cm (C O); MS (FD): m/z (%): 546.4 ([M] ,
100); elemental analysis calcd (%) for C39H62O (546.92): C 85.65, H 11.43;
found C 85.17, H 11.40.
4-Bromododecanoylbenzene (15): Dodecanoyl chloride (219 g, 231 mL,
1 mol) was added dropwise to a mixture of bromobenzene (314 g, 2 mol)
and aluminum chloride (160 g, 1.2 mol). The reaction mixture was then
stirred at 508C for 1 h, poured into ice water, and extracted with
dichloromethane. The organic phase was washed with HCl solution (2n)
and brine and dried over magnesium sulfate. After removal of the
solvent under vacuum, the residue was purified by recrystallization from
ethanol to afford 4-bromododecanoylbenzene (15) as colorless plates (yield
67%).
M.p. 648C. 1H NMR (300 MHz, CDCl3, 308C): d ˆ 7.73 (d, J ˆ 8.0 Hz, 2H),
7.52 (d, J ˆ 8.0 Hz, 2H), 2.83 (t, J ˆ 7.5 Hz, 2H), 1.63 (q, J ˆ 7.5 Hz, 2H),
1.31 ± 1.08 (m, 16H), 0.89 (t, J ˆ 7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3,
308C): d ˆ 199.8, 136.2, 132.2, 130.0, 128.3, 39.0, 32.3, 30.0, 29.9, 29.7, 24.7,
M.p. > 3008C. 1H NMR (300 MHz, CDCl3, 308C): d ˆ 7.66 (d, 3J(H,H) ˆ
3
8.0 Hz, 2H), 7.31 ± 7.23 (m, 12H), 6.89 ± 6.77 (m, 10H), 6.63 (d, J(H,H) ˆ
8.0 Hz, 2H); 13C NMR (75 MHz, CDCl3, 308C): d ˆ 142.3, 141.4, 138.7,
138.2, 138.0, 132.8, 131.7, 131.3, 129.3, 129.0, 128.1, 127.8, 127.7, 126.6, 124.5;
lmax (CHCl3, e) ˆ 373 (27500), 295 nm (69500); MS (FD): m/z (%): 506.6
‡
([M] , 100); elemental analysis calcd (%) for C40H26 (506.64): C 94.83, H
5.17; found C 94.83, H 5.14.
Chem. Eur. J. 2001, 7, No. 10
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0710-2203 $ 17.50+.50/0
2203

K. Müllen et al.
FULL PAPER
1
ˆ
7,8,9,10-Tetrakis(4-dodecylphenyl)fluoranthene (3b): A mixture of ace-
naphthylene (10) (0.4 g, 2.6 mmol) and tetra(4-dodecyl-phen-1-yl)cyclo-
pentadienone (9b) (3.0 g, 2.8 mmol) in xylene (20 mL) was refluxed for
16 h under an argon atmosphere. After cooling to room temperature,
ethanol (300 mL) was added to the reaction mixture. The precipitated solid
was filtered, washed with ethanol, and dried in vacuum. Subsequently, the
solid was dissolved in a refluxing mixture of acetone/benzene (1:5, 100 mL)
and treated with a solution of KMnO4 in acetone until the reaction mixture
remained purple. After filtration over a column of silica gel to remove
KMnO4, evaporation of the solvent, and drying in vacuum, 3b was
obtained as a yellow strongly fluorescent solid (yield 77%).
129.8, 129.7, 129.3, 122.8, 122.3; nÄ ˆ 1699 cm (C O); MS (FD): m/z (%):
‡
355.9 ([M] , 100); elemental analysis calcd (%) for C27H16O (356.42): C
90.99, H 4.52; found C 91.06, H 4.53.
7,9-Bis(4-dodecylphenyl)-8H-cyclopenta[l]acenaphthylen-8-one
(21b):
KOH/EtOH (3.5 mL) was added to a refluxing solution of acenaphthene-
quinone (20) (1.82 g, 10 mmol) and 1,3-bis(4-dodecylphenyl)-propan-2-one
(13b) (5.46 g, 10 mmol) in ethanol (10 mL) and toluene (1 mL). After five
minutes, the reaction mixture was cooled to 08C, and the precipitated
purple solid was filtered, washed with ethanol, and dried in vacuum (yield
86%).
M.p. 55 ± 568C. 1H NMR (300 MHz, CDCl3, 308C): d ˆ 8.06 (d, J(H,H) ˆ
3
1
3
M.p. 57 ± 588C. H NMR (300 MHz, CDCl3, 308C): d ˆ 7.63 (d, J(H,H) ˆ
8.0 Hz, 2H), 7.24 (dd, 3J(H,H) ˆ 8.0 Hz, 3J(H,H) ˆ 6.7 Hz, 2H), 7.17 (d,
3J(H,H) ˆ 7.3 Hz, 4H), 7.06 (d, 3J(H,H) ˆ 7.3 Hz, 4H), 6.73 (d, 3J(H,H) ˆ
8.0 Hz, 4H), 6.67 (d, 3J(H,H) ˆ 6.7 Hz, 2H), 6.63 (d, 3J(H,H) ˆ 8.0 Hz,
7.4 Hz, 2H), 7.89 (d, 3J(H,H) ˆ 8.6 Hz, 2H), 7.73 (d, 3J(H,H) ˆ 8.6 Hz, 4H),
7.61 (dd, 3J(H,H) ˆ 7.3 Hz, 3J(H,H) ˆ 8.6 Hz, 2H), 7.35 (d, 3J(H,H) ˆ
8.6 Hz, 4H), 2.70 (t, 3J(H,H) ˆ 7.4 Hz, 4H; a-CH2), 1.71 ± 1.29 (m, 40H;
CH2 ), 0.88 (t, 3J(H,H) ˆ 7.4 Hz, 6H; CH3); 13C NMR (75 MHz, CDCl3,
308C): d ˆ 203.3, 154.4, 144.5, 132.6, 129.9, 129.7, 129.5, 129.3, 128.4, 125.8,
122.6, 121.7, 36.8, 32.8, 32.4, 30.6, 30.5, 30.4, 30.3, 30.2, 23.6, 14.8; nÄ ˆ
3
3
2H), 2.61 (t, J(H,H) ˆ 7.3 Hz, 4H; a-CH2), 2.34 (t, J(H,H) ˆ 7.4 Hz, 4H;
a-CH2), 1.65 ± 1.15 (m, 80H; CH2 ), 0.89 (t, 3J(H,H) ˆ 6.7 Hz, 12H;
CH3); 13C NMR (75 MHz, CDCl3, 308C): d ˆ 142.3, 142.5, 140.7, 138.9,
138.8, 138.7, 138.6, 137.8, 132.7, 131.5, 131.2, 129.2, 128.9, 127.7, 127.4, 124.4,
36.7, 33.3, 32.5, 31.1, 31.0, 30.9, 30.7, 30.1, 24.1, 15.6; lmax (CHCl3, e) ˆ 375
1
‡
ˆ
1699 cm (C O); MS (FD): m/z (%): 695.3 ([M] , 100); elemental
analysis calcd (%) for C51H64O (693.06): C 88.31, H 9.31; found C 88.12, H
9.67.
‡
(26000), 298 nm (68000); MS (FD): m/z (%): 1179.7 ([M] , 100); elemental
analysis calcd (%) for C88H122 (1179.93): C 89.58, H 10.42; found C 89.35, H
10.69.
7,14-Diphenylacenaphtho[1,2-k]-fluoranthene (4a): A mixture of acenaph-
thylene (10) (1.16 g, 7.6 mmol) and 7,9-diphenyl-8H-cyclopenta[l]acenaph-
thylen-8-one (21a) (3 g, 8.4 mmol) in xylene (20 mL) was refluxed for 16 h
under an argon atmosphere. After cooling to room temperature, ethanol
(300 mL) was added to the reaction mixture. The precipitated solid was
filtered, washed with ethanol, and dried in vacuum. Subsequently, the solid
was dissolved in a refluxing mixture of acetone/benzene (1:5, 100 mL) and
treated with aliquots of a solution of KMnO4 in acetone until the reaction
mixture remained purple. After filtration over a column of silica gel to
remove KMnO4, evaporation of the solvent, and drying in vacuum, 4a was
obtained as a yellow, strongly fluorescent solid (yield 87%).
4,4',5,5',6,6',7,7'-Tetraphenyldiindeno[1,2,3-cd:1',2',3'-lm]perylene (5a): A
solution of FeCl3 (1.9 g, 11.7 mmol) in nitromethane (3 mL) was added
dropwise to a stirred solution of 7,8,9,10-tetraphenylfluoranthene (3a)
(506 mg, 1 mmol) in CH2Cl2 (40 mL). An argon stream was bubbled
through the reaction mixture throughout the entire reaction. After stirring
for another five minutes, the reaction was quenched with methanol
(40 mL). The precipitate was filtered, washed with methanol (40 mL), and
dried under reduced pressure. The crude product was purified by column
chromatography on silica gel with dichloromethane/petroleum ether (1:1)
to afford red 5a (yield: 90%).
M.p. > 3008C. 1H NMR (300 MHz, CDCl3, 308C): d ˆ 7.68 ± 7.60 (m, 14H),
3
3
7.30 (dd, J(H,H) ˆ 7.1 Hz, 4H), 6.67 (d, J(H,H) ˆ 6.9 Hz, 2H); 13C NMR
(75 MHz, CDCl3, 308C): d ˆ 140.8, 138.8, 138.3, 135.9, 134.8, 131.5, 131.3,
130.8, 130.1, 129.7, 128.3, 125.1; lmax (CHCl3, e) ˆ 423 (24900), 400 (18500),
M.p. > 3008C. 1H NMR (500 MHz, C2D2Cl4, 1308C): d ˆ 7.80 (d, 3J(H,H) ˆ
3
7.3 Hz, 4H), 7.30 ± 7.26 (m, 20H), 6.87 ± 6.78 (m, 20H), 6.55 (d, J(H,H) ˆ
7.3 Hz, 4H); 13C NMR (125 MHz, C2D2Cl4, 1308C): d ˆ 141.3, 140.2, 137.8,
137.2, 136.8, 134.8, 131.7, 130.5, 128.4, 127.2, 126.9, 125.6, 124.4, 122.2, 121.8;
lmax (CHCl3, e) ˆ 564 (86500), 523 (60150), 480 (25650), 316 (62500),
‡
309 nm (76570); MS (FD): m/z (%): 477.9 ([M] , 100); elemental analysis
calcd (%) for C38H22 (478.59): C 95.37, H 4.63; found C 95.45, H 4.70.
‡
275 nm (79500); MS (FD): m/z (%): 1008.9 ([M] , 100); elemental analysis
7,14-Bis[4-dodecylphenyl]acenaphtho[1,2-k]-fluoranthene (4b): A mixture
of acenaphthylene (10) (807 mg, 5.3 mmol) and 7,9-bis(4-dodecylphenyl)-
8H-cyclopenta[l]acenaphthylen-8-one (21b) (4 g, 5.8 mmol) in xylene
(15 mL) was refluxed for 16 h under an argon atmosphere. After cooling
to room temperature, ethanol (300 mL) was added to the reaction mixture.
The precipitated solid was filtered, washed with ethanol, and dried in
vacuum. Subsequently, the solid was dissolved in a refluxing mixture of
acetone/benzene (1:5, 100 mL) and treated with aliquots of a solution of
KMnO4 in acetone until the reaction mixture remained purple. After
filtration over a column of silica gel to remove KMnO4, evaporation of the
solvent, and drying in vacuum, 4b was obtained as a yellow, strongly
fluorescent solid (yield 83%).
calcd (%) for C80H48 (1009.26): C 95.21, H 4.79; found C 95.73, H 4.99.
Compound 5b: A solution of FeCl3 (1.7 g, 10 mmol) in nitromethane
(1.7 mL) was added dropwise to a stirred solution of 7,8,9,10-tetrakis(4-
dodecylphenyl)fluoranthene (3b) (500 mg, 0.4 mmol) in CH2Cl2 (40 mL).
An argon stream was bubbled through the reaction mixture throughout the
entire reaction. After stirring for another 30 min, the reaction was
quenched with methanol (50 mL). The precipitate was filtered, washed
with methanol (40 mL), and dried under reduced pressure. The crude
product was purified by column chromatography on silica gel with
dichloromethane/petroleum ether (1:1) to afford dark green 5b (yield:
45%).
M.p. > 3008C. 1H NMR (500 MHz, [D4]p-dichlorobenzene, 1558C): d ˆ
9.42 (d, 3J(H,H) ˆ 7.3 Hz, 4H), 8.87 (s, 4H), 8.84 (d, 3J(H,H) ˆ 7.8 Hz,
4H), 8.76 (s, 4H), 8.68 (s, 4H), 8.08 (d, 3J(H,H) ˆ 7.8 Hz, 4H), 7.65 (d,
3J(H,H) ˆ 7.3 Hz, 4H), 3.28 (t, 3J(H,H) ˆ 7.7 Hz, 8H; a-CH2), 3.18 (t,
3J(H,H) ˆ 7.7 Hz, 8 H ; a-CH2), 2.20 ± 1.44 (m, 160H; CH2 ), 1.00 (t,
3J(H,H) ˆ 7.1 Hz, 24 H ; CH3); lmax (CHCl3, e): 670 (98300), 615 (69500),
571 (29500), 458 (40500), 408 (79800), 346 nm (107100); MS (FD): m/z
M.p. > 3008C. 1H NMR (300 MHz, CDCl3, 308C): d ˆ 7.74 (d, 3J(H,H) ˆ
7.9 Hz, 4H), 7.58, 7.56 (d, 3J(H,H) ˆ 8.2 Hz, 8H), 7.35 (dd, 3J(H,H) ˆ 7.9 Hz,
3J(H,H) ˆ 6.8 Hz, 4H), 6.79 (d, 3J(H,H) ˆ 6.8 Hz, 4H), 2.90 (t, 3J(H,H) ˆ
9.0 Hz, 4H; a-CH2), 1.89 ± 1.30 (m, 40H; CH2 ), 0.89 (t, 3J(H,H) ˆ 6.7 Hz,
4H; CH3); 13C NMR (75 MHz, CDCl3, 308C): d ˆ 143.7, 137.6, 137.1,
136.8, 134.7, 133.6, 130.2, 130.1, 129.2, 128.1, 126.8, 123.6, 36.3, 32.4, 32.0,
30.2, 30.1, 30.0, 29.8, 29.7, 23.1, 14.3; lmax (CHCl3, e) ˆ 427 (26100), 403
‡
‡
(%): 2343.5 ([M] , 100); elemental analysis calcd (%) for C176H228
(2343.74): C 90.19, H 9.81; found C 89.88, H 9.67.
(17000), 313 nm (73200); MS (FD): m/z (%): 813.7 ([M] , 100); elemental
analysis calcd (%) for C62H70 (815.23): C 91.34, H 8.66; found C 91.10, H
8.73.
7,9-Diphenyl-8H-cyclopenta[l]acenaphthylen-8-one (21a): KOH/EtOH
(3 mL) was added to a refluxing solution of acenaphthenequinone (20)
(1.73 g, 9.5 mmol) and 1,3-diphenylpropane-2-one (13a) (2 g, 9.5 mmol) in
ethanol (10 mL) and toluene (1 mL). After five minutes, the reaction
mixture was cooled to 08C, and the precipitated purple solid was filtered,
washed with ethanol, and dried in vacuum (yield 94%).
M.p. > 3008C. 1H NMR (300 MHz, CDCl3, 308C): d ˆ 7.99 (d, 3J(H,H) ˆ
7.2 Hz, 2H), 7.83 (d, 3J(H,H) ˆ 8.3 Hz, 2H), 7.75 (d, 3J(H,H) ˆ 7.2 Hz, 4H),
7.55 (dd, 3J(H,H) ˆ 7.2 Hz, 3J(H,H) ˆ 8.3 Hz, 2H), 7.50 (dd, 3J(H,H) ˆ
7,2 Hz, 3J(H,H) ˆ 7.4 Hz, 4H), 7.39 (t, 3J(H,H) ˆ 7.4 Hz, 2H); 13C NMR
(75 MHz, CDCl3, 308C): d ˆ 203.0, 155.6, 146.1, 133.3, 132.5, 130.3, 130.0,
4,4',7,7'-Tetraphenyldiacenaphtho[1,2-k:1',2',k']diindeno[1,2,3-cd:1',2',3'-lm]-
perylene (22a): A solution of FeCl3 (2.04 g, 12.6 mmol) in nitromethane
(3 mL) was added dropwise to a stirred solution of 7,14-diphenylacenaph-
tho[1,2-k]-fluoranthene (4a) (1.0 g, 2.1 mmol) in CH2Cl2 (20 mL). An
argon stream was bubbled through the reaction mixture throughout the
entire reaction. After stirring for another ten minutes, the reaction was
quenched with methanol (40 mL). The precipitate was filtered, washed
with methanol (40 mL), and dried under reduced pressure. The crude
product was purified by column chromatography on silica gel with toluene
to afford blue 22a (yield: 85%).
2204
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0710-2204 $ 17.50+.50/0
Chem. Eur. J. 2001, 7, No. 10

Novel Perylene Chromophores
2197±2205
M.p. > 3008C. 1H NMR (500 MHz, C2D2Cl4, 1308C): d ˆ 7.83 (d, 3J(H,H) ˆ
[8] M. Müller, H. Mauermann-Düll, M. Wagner, V. Enkelmann, K.
Müllen, Angew. Chem. 1995, 107, 1751; Angew. Chem. Int. Ed. Engl.
1995, 34, 1583.
[9] A. Stabel, P. Herwig, K. Müllen, J. P. Rabe, Angew. Chem. 1995, 107,
1768; Angew. Chem. Int. Ed. Engl. 1995, 34, 1609.
3
7.7 Hz, 4H), 7.75 ± 7.71 (m, 24H), 7.30 (dd, J(H,H) ˆ 7.7 Hz, 4H), 6.72 (d,
3J(H,H) ˆ 7.7 Hz, 4H), 6.64 (d, 3J(H,H) ˆ 7.7 Hz, 4H); lmax (CHCl3, e) ˆ
601 (112000), 552 (70000), 513 (28300), 341 nm (116000); MS (FD): m/z
‡
(%): 952.2 ([M] , 100); elemental analysis calcd (%) for C76H40 (953.15): C
95.48, H 4.52; found C 95.26, H 4.37.
[10] V. S. Iyer, M. Wehmeier, J. D. Brand, M. A. Keegstra, K. Müllen,
Angew. Chem. 1997, 109, 1675; Angew. Chem. Int. Ed. Engl. 1997, 36,
1603.
[11] P. Herwig, C. W. Kayser, K. Müllen, H. W. Spiess, Adv. Mater. 1996, 8,
510.
4,4',7,7'-Tetrakis(4-dodecylphenyldiacenaphtho) [1,2-k:1',2',k']diindeno-
[1,2,3-cd:1',2',3'-lm]perylene (22b): A solution of FeCl3 (0.6 g, 3.7 mmol)
in nitromethane (1 mL) was added dropwise to a stirred solution of 7,14-
bis[4-dodecylphenyl]acenaphtho[1,2-k]-fluoranthene
(4b)
(0.5 g,
[12] B. F. Plummer, L. K. Steffen, T. L. Braley, W. G. Resse, K. Zych, G.
Van Dyke, B. Tulley, J. Am. Chem. Soc. 1993, 115, 11542.
[13] F. Gräser, E. Hädicke, Liebigs Ann. Chem. 1980, 1995.
[14] Y. Nagao, T. Misono, Dyes Pigm. 1984, 5, 171.
[15] R. Gvishi, R. Reisfeld, Z. Bursheim, Chem. Phys. Lett. 1993, 213, 338.
[16] D. Schlettwein, D. Wöhrle, E. Karmann, U. Melville, Chem. Mater.
1994, 6, 3.
[17] M. P. OꢁNeill, M. P. Niemczyk, W. A. Svec, D. Gosztola, G. L.
Gaines III, M. R. Wasielewski, Science, 1992, 257, 63.
[18] F. A. Holtrup, G. R. J. Müller, H. Quante, S. De Feyter, F. C.
De Schryver, K. Müllen, Chem. Eur. J. 1997, 3, 219.
[19] Y. Geerts, H. Quante, R. Mahrt, M. Hopmeier, A. Böhm, K. Müllen, J.
Mater. Chem. 1998, 8, 2357.
[20] F. O. Holtrup, G. R. J. Müller, J. Uebe, K. Müllen, Tetrahedron, 1997,
20, 6847.
[21] R. Johnson, O. Grummit, Org. Synth. 1943, 23, 92.
[22] Y. Kimura, Y. Tomito, S. Nakanishi, Y. Otsuji, Chem. Lett. 1979, 321.
[23] H. des Abbayes, J. Clement, P. Laurent, G. Tanguy, N. Thilmont,
Organometallics 1988, 7, 2293.
0.53 mmol) in CH2Cl2 (10 mL). An argon stream was bubbled through
the reaction mixture throughout the entire reaction. After stirring for
another ten minutes, the reaction was quenched with methanol (40 mL).
The precipitate was filtered, washed with methanol (40 mL), and dried
under reduced pressure. The crude product was purified by column
chromatography on silica gel with toluene to afford blue 22b (yield: 87%).
M.p. > 3008C. 1H NMR (500 MHz, C2D2Cl4, 1308C): d ˆ 7.83 (d, 3J(H,H) ˆ
7.7 Hz, 4H), 7.66 (d, 3J(H,H) ˆ 8.0 Hz, 4H), 7.58, 7.51 (d, 3J(H,H) ˆ 7.6 Hz,
16H), 7.29 (dd, 3J(H,H) ˆ 7.6 Hz, 3J(H,H) ˆ 8.0 Hz, 4H), 6.81 (d,
3J(H,H) ˆ 7.6 Hz, 4H), 6.64 (d, 3J(H,H) ˆ 7.7 Hz, 4H), 2.90 (t, 3J(H,H) ˆ
7.5 Hz, 8H; a-CH2), 1.88 ± 1.31 (m, 80H; Calkyl), 0.88 (t, 3J(H,H) ˆ 7.7 Hz,
CH3); 13C NMR (75 MHz, C2D2Cl4, 1308C): d ˆ 143.5, 137.9, 137.6, 137.4,
136.9, 134.9, 134.0, 130.9, 129.8, 129.6, 128.1, 126.6, 125.7, 124.5, 123.6, 122.2,
36.1, 32.0, 31.5, 29.9, 29.8, 29.7, 29.5, 29.4, 22.7, 13.9; lmax (CHCl3, e) ˆ 602
(114000), 555 (75000), 517 (29700), 339 nm (119600); MS (FD): m/z (%):
‡
1624.5 ([M] , 100); elemental analysis calcd (%) for C124H136 (1626.44): C
91.57, H 8.420; found C 91.45, H 8.35.
[24] U. T. Mueller-Westerhoff, M. Zhou, J. Org. Chem. 1994, 59, 4988.
[25] R. Scholl, C. Seer, R. Weitzenböck, Chem. Ber. 1910, 43, 2202.
[26] A. McKillop, A. G. Turrell, D. W. Young, E. C. Taylor, J. Am. Chem.
Soc. 1980, 102, 6504.
[27] S. Ito, P. T. Herwig, T. Böhme, J. P. Rabe, W. Rettig, K. Müllen, J. Am.
Chem. Soc. 2000, 122, 7698.
Acknowledgements
Financial support of the Volkswagenstiftung and the Fonds der Chemie is
gratefully acknowledged.
[28] P. Kovacic, J. Oziomek, J. Org. Chem. 1964, 29, 100.
[29] P. Kovacic, F. W. Koch, J. Org. Chem. 1963, 28, 1864.
[30] J. D. Debad, J. C. Morris, V. Lynch, P. Magnus, A. J. Bard, J. Am.
Chem. Soc. 1996, 119, 2374.
[31] W. Dilthey, G. Hurtig, Ber. Dtsch. Chem. Ges. A 1934, 67, 2004.
[32] J. D. Debad, A. J. Bard, J. Am. Chem. Soc. 1998, 120, 2476.
[33] A. Zinke, Mh. Chem.-Zh. 1962, 95, 1117.
[1] R. Faust, Angew. Chem. 1995, 107, 1562; Angew. Chem. Int. Ed. Engl.
1995, 34, 1429.
[2] L. T. Scott, M. M. Hashemi, D. T. Meyer, H. B. Warren, J. Am. Chem.
Soc. 1991, 113, 7082.
[3] R. D. Broene, F. Diederich, Tetrahedron Lett. 1991, 32, 5227.
[4] J. C. Fetzer, W. C. Biggs, Polycyclic Aromat. Compd. 1994, 4, 3.
[5] F. Doetz, J. D. Brand, S. Ito, L. Gherghel, K. Müllen, J. Am. Chem.
Soc. 2000, 122, 7707.
[34] B. Schlicke, J. Frahn, A. D. Schlüter, Synth. Met. 1996, 83, 173.
[6] D. Adam, P. Schuhmacher, J. Simmerer, L. Häussling, K. Siemens-
meyer, H. Ringsdorf, D. Haarer, Nature, 1994, 371, 141.
[7] H. Zollinger, Color Chemistry, VCH, Weinheim, 1987.
Received: May 12, 2000
Revised version: October 25, 2000 [F2482]
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