Cyclodehydrogenation of poly(perylene) to poly(quaterrylene): Toward poly(peri-naphthalene)

Article abstract of DOI:10.1021/ma011724d

Cyclodehydrogenation of soluble polyperylenes gives polymers containing predominantly quaterrylene units by spectral analysis. Evidence for larger rylene units is also seen. These polymers represent important intermediates toward a poly(peri-naphthalene) (PPN). Reactions on model compounds suggest that the insolubility of polymers with larger rylene units is predominantly due to the rigidity of the polymer backbone.

Full text of DOI:10.1021/ma011724d

1576
Macromolecules 2002, 35, 1576-1582
Cyclodehydrogenation of Poly(perylene) to Poly(quaterrylene): Toward
Poly(peri-naphthalene)
Ca r sten F or m er , Stefa n Beck er , An d r ew C. Gr im sd a le, a n d Kla u s Mu1 llen *
Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
Received October 2, 2001; Revised Manuscript Received November 29, 2001
ABSTRACT: Cyclodehydrogenation of soluble polyperylenes gives polymers containing predominantly
quaterrylene units by spectral analysis. Evidence for larger rylene units is also seen. These polymers
represent important intermediates toward a poly(peri-naphthalene) (PPN). Reactions on model compounds
suggest that the insolubility of polymers with larger rylene units is predominantly due to the rigidity of
the polymer backbone.
In tr od u ction
better solubilizing groups groups,7 our approach was to
repeat these experiments with the perylene monomer
10 which carries four solubilizing tert-octylphenoxy
groups in the bay positions.
Theoretical works conclude that poly(peri-naphtha-
lene) (PPN) (4a ) (Scheme 1) is expected to have a very
small band gap and thus to be an intrinsic electrical
conductor.1 The origin of this behavior is the ladder-
type conjugated structure leading to a more rigid
backbone than those of other electroactive conjugated
polymers such as poly(p-phenylenevinylene) (PPV) or
poly(p-phenylene) (PPP). This rigidity leads to a greater
degree of planarity and corresponding greater delocal-
ization of electron wave functions. It also reduces the
susceptibility of the structure to local distortions upon
excitation by minimizing the degree of ring-rotational
freedom and inhibiting Peierls distortion through bond
length alteration by inclusion of all the CC bonds in
aromatic rings.2 Because of its insolubility, PPN has yet
to be synthesized and characterized, and calculations
could only be correlated with a series of oligorylenes
2a -d (Scheme 1).3-5 While the tetraalkylperylene 2a
is readily soluble in organic solvents, solubility de-
creases with increasing length so that the pentarylene
2d is only slightly soluble even in boiling chloroben-
zene.3 The extrapolation of the longest wavelength
absorption band of these oligomers with increasing
chain length results in a theoretical optical band gap of
0.93-0.98 eV for the polymer PPN (4a ).3 This small gap
is the reason for its expected intrinsic semiconductivity,
making PPN a potentially extremely interesting poly-
mer. Because of its expected insolubility, chemically
regular PPN may not become available in the future;
the choice of the right solubilizing groups might however
permit preparation and characterization of a soluble
polymer with a PPN backbone, hence possessing similar
electronic properties as PPN. Our approach toward such
a polymer is to synthesize a soluble poly(perylene) which
could be converted to a PPN by a polymer analogous
cyclodehydrogenation reaction. Such a reaction has
previously been used by us for the conversion of bi-
(perylene) to quaterrylene 2c.3-5
Resu lts a n d Discu ssion
The synthesis of perylene 10 can be performed start-
ing from 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracar-
boxylic acid dianhydride (5) (Scheme 2). Reaction with
cyclohexylamine gave the corresponding diimide 6 in
88% yield. The solubilizing phenoxy groups were then
attached byreaction ofthe tetrachloride 6 with 4-(1′,1′,3′,3′-
tetra-
methylbutyl)phenol in the presence of potassium car-
bonate in 65% yield. Hydrolysis of the diimide 7 under
basic conditions produced the dianhydride 8 in 65%
yield. Decarboxylation of the anhydride then afforded
the perylene 9 (65% yield), which was then brominated
resulting almost quantitatively in the perylene mono-
mer 3,9-(3,10)-dibromo-1,6,7,12-tetrakis[4-(1,1,3,3-tet-
ramethylbutyl)phenoxy]perylene (10). This monomer is
a 1:1 inseparable mixture of the 3,9- and 3,10-dibromo
isomers. As has previously been shown,6 the use of such
a mixture presents no problems in polymerization as
the two isomers are of equal reactivity. Polymerization
of 10 under Yamamoto conditions led to the poly-
(perylene) 3a which could be purified by precipitation
from a solution of methanol/acetone/2 N HCl (5:5:1) to
yield 73% of a yellow-greenish polymer. 1H NMR
investigation revealed broad signals at δ (ppm) 7.00,
6.84, 6.45, 1.40, 1.03, and 0.44. Gel permeation chro-
matography (GPC) using polystyrene calibration gave
a number-average molecular weight (Mn) of 27 000 and
a weight-average molecular weight (Mw) of 99 000
(Figure 5) corresponding to a degree of polymerization
(Pn) of about 27. This molecular weight is about 3 times
larger than that of the earlier poly(perylene) 3b, due to
the better solubilizing groups. Although less commonly
used in the literature, the molecular weight of a rigid
polymer as poly(perylene) 3a with a poly(p-phenylene)
(PPP) backbone can be expressed more accurately by
application of a PPP calibration. This resulted for
polymer 3a in a Mn of 19 000 and a Mw of 51 000. The
shape of the UV-vis spectrum of 3a is similar to that
of 3b. The absorption maximum is however shifted to
489 nm (cf. 3b: 443 nm). This bathochromic shift might
be due to 3a possesssing a longer conjugation length
than 3b. The bathochromic shift compared to perylene
2a can be explained from the greater conjugation length
Poly(perylene) 3b has been previously synthesized by
Yamamoto polycoupling of a dibromoperylene mono-
mer.6 However, the low solubility of 3b in DMF resulted
in a low number-average molecular weight Mn of 10 540
(Mw ) 27 220). It was therefore concluded that tert-
butylphenoxy substituents did not introduce enough
solubility to enable higher molecular weights.6 Since
tert-octylphenoxy substituents have proven to be much
* Corresponding author. E-mail: muellen@mpip-mainz.mpg.de.
10.1021/ma011724d CCC: $22.00 © 2002 American Chemical Society
Published on Web 01/29/2002

Macromolecules, Vol. 35, No. 5, 2002
Cyclodehydrogenation of Poly(perylene) 1577
Sch em e 1. P er ylen e (1), Oligor ylen es 2a -d , P oly(p er ylen e)s 3a ,b, a n d P P Ns 4a ,b
and also from the electron pushing effect of the phenoxy
groups.
assigned to a small amount of octarrylene units in the
polymer which might be formed by peri-condensation
of two quaterrylene units. Further evidence for this
assignment can be found by relating the optical transi-
tion energies to the reciprocal chain length of the
corresponding rylene units in the polymer chain. Ex-
trapolation of oligomer properties to indefinite chain
length is a commonly used approach to estimate poly-
mer characteristics in order to compare the extrapolated
results with the experimental values of a polymer and
especially to forecast properties of polymers that are not
accessible due to insolubility.2 Karabunarliev et al.2
investigated a series of oligorylenes 2a -d (optical
transition energies: 2.830, 2.209, 1.872, and 1.657 eV)
and plotted the optical transition energies as a function
of the reciprocal chain length. The experimental results
are displayed together with calculated results (PPP-SCI
calculation) and the absorption maxima of polyperylene
3a , polyquaterrylene 11, and the second absorption
maximum of 11 in Figure 1. It is very probable that the
latter can be assigned to octarylene blocks within the
polymer chain because the corresponding data point is
located exactly on the line extrapolated from the other
data points. It is obvious that electronic transitions
originating from the polymer occur at smaller energies
compared to electronic transitions of the corresponding
oligorylenes. Remarkably, extrapolation to infinite num-
ber of rylene units from these data gives the same value
of 0.95 eV for the polymer as was obtained from the
series of oligomers. This result is reasonable when
considering that a difference in conjugation length
between 4a and 4b is no longer seen for 1/n ) 0.
Furthermore, this observation might suggest that elec-
tron-donating phenoxy groups would have a negligible
effect on the band gap of a PPN 4b.
Compared to polynaphthalene, poly(perylene) 3a con-
stitutes a better precursor for achieving a polymer with
extended rylene structure since every second naphtha-
lene unit is already peri-condensed. To achieve PPN, (i)
the availability of a dehydrogenation method as quan-
titative as possible and (ii) a sufficient solubility of the
resulting PPN is crucial. We applied several methods
that are well-known from the literature to obtain
dehydrogenation: (i) sulfur in toluene (oxidation poten-
tial: +0.142 V8), (ii) aluminum chloride/copper(II) chlo-
ride in carbon disulfide (+0.153 V, Kovacic conditions9),
(iii) iodine in toluene (+0.536 V8), (iv) p-benzoquinone
in toluene (+0.699 V8), (v) iron(III) chloride in ni-
tromethane-dichloromethane (+0.771 V8), and (vi) 5,6-
dichloro-2,3-dicyano-p-benzoquinone in toluene (DDQ,
ca. +1 V10). Kovacic conditions have previously been
successfully used for the synthesis of oligo(peri-naph-
thylene)s 2a -d starting from oligo(1,4-naphthylene)s.3
Treatment of 3b with sulfur, p-benzoquinone and
DDQ did not lead to any reaction. However, dehydro-
genation occurred under Kovacic conditions as well as
from the reaction with iodine and with iron(III) chloride
as was shown by the color of the reaction mixtures
becoming greenish. The isolated products were charac-
terized by their UV absorption spectra. The reaction of
3b with iron(III) chloride as well as with iodine led
almost quantitatively to a poly(quaterrylene) 11 (Scheme
3). This was concluded from the loss of the typical
perylene absorption band at 489 nm of 3b (Figure 2)
and the appearance of a typical quaterrylene absorption
(Figure 3). The absorption maximum of 713 nm shows
a bathochromic shift compared to quaterrylene 2c (662
nm) (Figure 4). As in the case of 3a and 2a , this shift
can be explained by a larger conjugation length and the
electron-donating effect of the phenoxy groups.
The absorption, excitation, and fluorescence spectra
of poly(perylene) 3a and poly(quaterrylene) 11 are
displayed in Figures 2 and 3, respectively. The absorp-
tion maxima of 3a and 11 are found at 489 and 713 nm,
respectively.
Remarkably, the dehydrogenation seems to stop at
the stage of a quaterrylene. A further weak absorption
with a maximum of 939 nm (Figure 3) can probably be

1578 Former et al.
Macromolecules, Vol. 35, No. 5, 2002
Sch em e 2. Syn th esis of th e P oly(p er ylen e) 3a : (a ) NMP , CH3COOH, Cycloh exyla m in e; (b)
4-(1′,1′,3′,3′-Tetr a m eth ylbu tyl)p h en ol, K2CO3, NMP ; (c) KOH, 2-P r op a n ol, H2O; (d ) Cu 2O, Cu , qu in olin e; (e) NBS,
DMF ; (f) (1) Ni(COD)2, 2,2′-Bip yr id in e, COD, DMF /Tolu en e, (2) Br om oben zen e
Sch em e 3. Oxid a tion of P oly(p er ylen e) 3a to P oly(qu a ter r ylen e) 11 w ith Iod in e in Tolu en e or w ith F eCl3 in
CH3NO2 a n d CH2Cl2
As can be seen from Figure 4, the absorption spectra
for the polymers closely resemble those for the mono-
mers, but with a bathochromic shift.
The GPC traces of poly(perylene) 3a and poly(qua-
terrylene) 11 are displayed in Figure 5. Although 3a
and 11 should possess the same chain length, the
number- and weight-average molecular weights of 11
(Mn ) 41 000, Mw ) 112 000) seem to be higher than
the ones of the “precursor” 3a (Mn ) 7000, Mw ) 9000).
This is to be expected since 11 has a much more rigid
backbone than 3a and thus has an increased hydrody-
namic volume for chains with the same chain length.
The resulting shift of the GPC trace to shorter retention
times of 11 compared to 3a is visualized in Figure 5.

Macromolecules, Vol. 35, No. 5, 2002
Cyclodehydrogenation of Poly(perylene) 1579
F igu r e 1. Band gap (eV) (calculated from UV absorption) as
a function of the number of rylene units of oligorylenes 2a -d
(experimental (9) and calculated (0) values) and polymers 3a
and 11 (b).
F igu r e 4. UV spectra (chloroform) of (from left to right)
bisperylene 13, poly(perylene) 3a , quaterrylene 14, and poly-
(quaterrylene) 11.
F igu r e 2. Absorption, excitation (dashes), and fluorescence
spectra of poly(perylene) 3a .
F igu r e 5. GPC traces (THF) of poly(perylene) 3a (solid line)
and poly(quaterrylene) 11 (dashed line).
iodine produced small insoluble fractions. Kovacic con-
ditions resulted in a polymer that showed UV absorption
originating from perylene and quaterrylene units in
about equal intensities. Heating of the reaction mixture
to 60 °C gave a clear solution with an insoluble fraction.
This observation could be caused by two effects. On one
hand, formation of further ring closures within poly-
(quaterrylene) 11 might result in insufficient solubility
due to increased rigidity of the polymer. On the other
hand, more drastic conditions might cause a loss of
solubilizing phenoxy groups.
To test this, we prepared the biperylene 13 and
subjected it to the same reaction conditions. Bromina-
tion of 9 gave a crude product which field desorption
mass spectrometry (FD-MS) revealed to be a mixture
of perylene 9 (relative intensity 100), 3-bromo-1,5,7,12-
tetrakis[4-(1,1,3,3-tetramethylbutyl)phenoxy]perylene (12)
(50), and 3,9-(3,10)-bromoperylene 10 (15), which was
subjected to Yamamoto coupling without further puri-
fication. FD-MS of ther resulting crude product revealed
a mixture of perylene 9 (relative intensity 100), ca. 60%
(13) (60), and a triperylene (65). The desired product
13 was obtained in 4% overall yield by column chroma-
tography on silica eluting with hexane/dichloromethane
(8:1). Reaction of biperylene 13 with iodine in toluene
at 60 °C or with iron(III) chloride produced the quater-
rylene 14 (Scheme 4). Investigation of this quaterrylene
14 showed only a negligible loss of phenoxy groups. This
F igu r e 3. Absorption, excitation (dashes), and fluorescence
spectra of poly(quaterrylene) 11.
As mentioned above, for rigid polymer chains as 3a and
11 GPC with poly(p-phenylene) calibration should lead
to more accurate values. For 11 the number- and
weight-average molecular weights are Mn ) 26 000 and
Mw ) 57 000.
One might anticipate that more drastic reaction
conditions would result in a further condensation of
rylene blocks. However, when the reaction mixtures
were refluxed for a longer time, the absorption of 11 at
939 nm did not increase. Instead, the reaction with

1580 Former et al.
Macromolecules, Vol. 35, No. 5, 2002
Sch em e 4. Syn th esis of Mod el Com p ou n d s 3,3′-Bip er ylen e 13 a n d Qu a ter r ylen e 14: (a ) NBS, DMF ; (b) Ya m a m oto
Cou p lin g; (c) Ir on (III) Ch lor id e in CH3NO2/CH2Cl2
6: mp >300 °C. 1H NMR (500 MHz, CDCl3, 25 °C): δ (ppm)
outcome suggests that stiffness of the polymer backbone
) 8.62 (s, 4H), 4.98 (m, 2H), 2.50 (m, 4H), 1.83 (m, 8H), 1.72
(m, 8H). 13C NMR (125 MHz, CD2Cl2, 25 °C): δ (ppm) ) 162.63
(CdO), 135.29, 132.87, 131.41, 128.39, 123.79, 123.34, 54.29,
26.48, 25.35. FD-MS: m/z (u e0-1) ) 692.4 (100%, M+) (calcd:
692.41). FT-IR: ν ) 1700 (νCdO); 1665 cm-1 (νCdO). UV
(CHCl3): λmax (ꢀ) ) 322 (3645); 426 (10231); 484 (26 883); 516
nm (35 024 L mol-1 cm-1). Anal. Calcd for C36H26Cl4N2O4: C,
62.45; H, 3.78; N, 4.05. Found: C, 61.97; H, 3.75; N, 4.20.
is the dominant cause of insolubility of materials with
PPN fragments larger than quaterrylene blocks within
the polymer chains. Reaction of 13 under Kovacic
conditions resulted in an unidentified insoluble product.
These results suggest that prepartion of a PPN by this
route may be infeasible unless the solubility can be
further improved.
N ,N ′-Dicycloh e xyl-1,6,7,12-t e t r a k is[4-(1,1,3,3-t e t r a -
m et h ylb u t yl)p h en oxy]p er ylen e-3,4,9,10-t et r a ca r b oxyl-
ic Acid Diim id e (7). N,N′-Dicyclohexyl-1,6,7,12-tetrachloro-
perylene-3,4,9,10-tetracarboxylic acid diimide (6) (10 g, 14.4
mmol), 4-(1′,1′,3′,3′-tetramethylbutyl)phenol (29.8 g, 14.4 mmol),
and potassium carbonate (9.98 g, 72.2 mmol) were suspended
in NMP (720 mL) under an argon atmosphere. The suspension
was stirred at 120 °C. The conversion was controlled by
monitoring the change in color from orange red to dark red
violet and the disappearance of the insoluble fraction. After 8
h the reaction was complete; after cooling to room temperature
the solution was poured into a stirred mixture of H2O/
concentrated HCl (11:1, 300 mL), and the precipitate was
collected and washed with water. The dried product was
purified by chromatography on silica column eluting with
dichloromethane/hexane 1:1. The resulting dark red solid was
dried under vacuum at 65 °C (yield: 12.84 g, 64.8%).
Con clu sion s
We have shown that by using superior solubilizing
groups the molar mass of polyperylenes as potential
intermediates in the synthesis of PPN can be improved
significantly. These can be cyclodehydrogenated at every
second perylene unit to give a poly(quaterrylene) in
nearly quantitative yield. Some evidence for formation
of longer rylene units was also seen. Application of
stronger dehydration methods in attempts to get closer
to a PPN structure produced insoluble materials. Reac-
tions on model compounds suggest that the dominant
cause of insolubility, when PPN fragments within the
polymer chains become larger than quaterrylene blocks,
is the rigidity of the backbone.
1
7: mp 241 °C. H NMR (500 MHz, CDCl3, 25 °C): δ (ppm)
Exp er im en ta l Section
3
3
) 8.07 (s, 4 H), 7.19 (d, J ) 8.77 Hz, 8 H), 6.78 (d, J ) 8.77
Hz, 8 H), 4.86 (m, 2 H), 2.42 (m, 4 H), 1.78 (m, 8 H), 1.65 (m,
8 H), 1.61 (s, 8 H, CH2), 1.29 (s, 24 H, (CH3)2), 0.71 (s, 36 H,
(CH3)3). 13C NMR (75 MHz, CD2Cl2, 25 °C): δ (ppm) ) 162.78
(CdO), 155.10, 151.72, 145.58, 131.65, 126.61, 122.02, 119.29,
118.97, 118.66, 118.48, 56.09, 52.91, 37.35, 31.43, 30.87, 30.51,
28.14, 25.49, 24.42. FD-MS: m/z (u e0-1) ) 1372.0 (100%, M+)
(calcd:1371.87). FT-IR: ν ) 2953, 2872, 1700 (νCdO), 1661 (νCd
O), 1588, 1503, 1412, 1337, 1296, 1217, 1176, 1148, 1015, 984,
873, 836, 806, 584 cm-1. UV (CHCl3): λmax (ꢀ) ) 368 (4132);
449 (17 098); 540 (26 652); 578 nm (42 734 L mol-1 cm-1). Anal.
Calcd for C92H110N2O8: C, 80.55; H, 8.08; N, 2.04. Found: C,
80.51; H, 8.09; N, 2.13.
1,6,7,12-Tetrachloroperylene-3,4,9,10-tetracarboxylic acid
dianhydride was obtained from BASF-AG, Ludwigshafen.
Other reagents were purchased from Aldrich. GPC was
performed in THF against polystyrene or functionalized poly-
(p-phenylene)11 standards on a Waters 717 with autosampler.
N,N’-Dicycloh exyl-1,6,7,12-tetr ach lor oper ylen e-3,4,9,10-
t et r a ca r b oxylic Acid Diim id e (6). 1,6,7,12-Tetrachloro-
perylene-3,4,9,10-tetracarboxylic acid dianhydride (5) (20 g,
37.8 mmol) was dissolved in N-methyl-2-pyrrolidinone (NMP)
(300 mL), and glacial acetic acid (14 g) was added to the stirred
solution. Cyclohexylamine (11.11 g, 112 mmol) was then added
slowly, and the solution was stirred under argon for 6 h at 90
°C. During this time a change of color to orange was observed.
The solution was cooled to room temperature, and the orange-
red solid product was isolated and washed with methanol. The
yield was 22.9 g (87.7%).
1,6,7,12-Tetr a k is[4-(1,1,3,3-tetr a m eth ylbu tyl)p h en oxy]-
p er ylen e-3,4,9,10-tetr a ca r boxylic Acid Dia n h yd r id e (8).
The diimide 7 (11.8 g, 8.6 mml), potassium hydroxide (250 g),
2-propanol (1.7 L), and water (170 mL) were heated under

Macromolecules, Vol. 35, No. 5, 2002
Cyclodehydrogenation of Poly(perylene) 1581
reflux in a 4 L flask for 12 h. During the reaction, the color
changed from red to green due to the formation of the
tetraanion of 8. The solution was cooled to room temperature
and poured into a mixture of H2O/concentrated HCl (10:1, 2
L) which was accompanied by a change in color to red. After
2 h the precipitation was completed, and the product was
washed with water and recrystallized from dichloromethane/
methanol (1:1) (yield: 12.84 g, 64.8%).
residue in toluene (6 mL) the polymer was precipitated from
a mixture of methanol/acetone/2 N HCl (5:5:1, 200 mL). The
polymer was obtained as a brown-greenish powder (210 mg,
73%).
3a : 1H NMR (500 MHz, THF, 25 °C): δ (ppm) ) 7.00, 6.84,
6.45 (3 × m, 22 H), 1.40, 1.03, 0.44 (3 × m, 68 H). GPC (THF,
1 g/L, 30 °C): Mn 27 000, Mw 99 000 (polystyrene calibration),
Mn 19 000, Mw 51 000 (poly(p-phenylene) calibration). UV abs-
(CHCl3): λmax(ꢀ) ) 489 nm (29 100 L/mol cm). UV fluor(CHCl3,
exc at 470 nm): λmax ) 554 nm. DSC (20 K/min): glass
transition at 208 °C (0.159 J /(g K)). TGA (20 K/min): 5%
degradation at 376 °C, maximum degradation (29%) at 422
°C. Anal. Calcd for (C76H90O4): C, 85.5; H, 8.5. Found: C, 80.7;
H, 9.3.
8: mp 250 °C. 1H NMR (250 MHz, C2D2Cl4, 25 °C): δ (ppm)
) 7.99 (s, 4 H), 7.23 (d, 3J ) 9.3 Hz, 8 H), 6.82 (d, 3J ) 9.2 Hz,
8 H), 1.68 (s, 8 H), 1.28 (s, 24 H), 0.68 (m, 36 H); FD-MS: m/z
(u e0-1) ) 1209.2 (100%, M+) (calcd:1209.55). FT-IR: 3448,
2952, 1744 (νCdO), 1588 (νCdO), 1502, 1350, 1337, 1288, 1213,
1136, 1015, 820, 798, 737 cm-1. Anal. Calcd for C80H88O10: C,
79.44; H, 7.33. Found: C, 79.40; H, 7.51.
P oly(qu a ter r ylen e) 11. The poly(perylene) 3a (20 mg, 0.02
mmol) was placed in a Schlenk tube under an argon atmo-
sphere and dissolved in dichloromethane (5 mL). After addition
of iron(III) chloride (60 mg, 0.34 mmol) and nitromethane (0.3
mL) the solution was stirred at room temperature for 2 h and
then refluxed for 7 days with monitoring by UV-vis spectros-
copy. Methanol (10 mL), water (20 mL), and dichloromethane
(50 mL) were added to the solution. The organic layer was
dried over magnesium sulfate, and the solvent was removed
under reduced pressure to give the poly(quaterrylene) 11.
Alternatively, 3a was converted to 11 by oxidative dehy-
drogenation with iodine in toluene. Excess iodine was removed
by addition of toluene and washing the organic layer with
sodium thiosulfate solution. 11: GPC (THF, 1 g/L, 30 °C)
(Figure 5): Mn 41 000, Mw 112 000 (polystyrene calibration),
Mn 26 000, Mw 57 000 (poly(p-phenylene) calibration). UV abs-
(CHCl3): λmax ) 713 nm; UV fluor(CHCl3, exc at 700 nm): λmax
) 744 nm. Anal. Calcd for (C152H178O8): C, 85.6; H, 8.4.
Found: C, 78.8; H, 8.6.
3,3′-Bip er ylen e 13. 1,6,7,12-Tetrakis[4-(1,1,3,3-tetrameth-
ylbutyl)phenoxy]perylene (9) (100 mg, 0.09 mmol) was dis-
solved in DMF (2 mL). After addition of NBS (18 mg, 0.09
mmol) the solution was stirred for 24 h at 70 °C to give a crude
mixture of products which was used without further purifica-
tion. Bis(cyclooctadiene)nickel(0) (17 mg, 0.06 mmol), 2,2′-
bipyridine (10 mg, 0.06 mmol), and cyclooctadiene (0.03 mL)
were dissolved in dimethylformamide (1.5 mL) in a Schlenk
tube under glovebox conditions. The solution was heated to
80 °C for 20 min, and a solution of the above crude product
mixture (70 mg) in toluene (1 mL) was added. The resulting
crude product was then absorbed onto on silica. Elution with
hexane/dichloromethane (8:1) gave the desired product 13 (8
mg, 4%).
13: 1H NMR (300 MHz, CDCl3, 25 °C): δ (ppm) ) 7.39-
7.04 (m, 46 H), 1.75, 1.40, 1.03, 0.95, 0.51 (5 × m, 136 H). UV
(CHCl3): λmax ) 471 nm. FD-MS: m/z (u e0-1) ) 2136.7 (100%,
M+) (calcd for C152H182O8: 2137.1), 1931.7 (7%, M+-O(C6H4)-
(C8H17)).
Qu a ter r ylen e 14. 3,3′-Biperylene 13 (2 mg) was placed in
a Schlenk tube together with iron(III) chloride (5 mg), ni-
tromethane (0.1 mL), and dichloromethane (1 mL). The
solution was stirred for 24 h and then worked up as in the
preparation of poly(quaterrylene) 11.
14: 1H NMR (300 MHz, CDCl3): δ (ppm) ) 7.39-7.04 (m,
46 H), 1.60, 1.40, 1.02, 0.85, 0.35, 0.27 (6 × m, 136 H). UV
(CHCl3): λmax 673 nm (100%) and 621 nm (67%). FD-MS: m/z
) 2135.0 (100%, M+) (calcd for C152H180O8: 2135.1), 1931.6 (7%,
M+-O(C6H4)(C8H17)).
1,6,7,12-Tetr a k is[4-(1,1,3,3-tetr a m eth ylbu tyl)p h en oxy]-
p er ylen e (9). A mixture of the anhydride 8 (15 g, 12.4 mmol),
copper(I) oxide (10 g), copper powder (1 g), and quinoline (700
mL) was heated to 220 °C for 8 h under an argon atmosphere.
Half of the solvent was removed under reduced pressure, and
the residue was poured into a stirred mixture of H2O/
concentratedHCl (10:1, 2.5 L). The resulting yellow precipitate
was washed with water and purified by chromatography on
silica eluting with dichloromethane/n-hexane (1:2) (yield: 8.62
g, 65%).
9: mp 176-178 °C. 1H NMR (500 MHz, THF, 306 K): δ
3
3
(ppm) ) 7.62 (d, J ) 5.5 Hz, 4 H), 7.24 (d, J ) 5.8 Hz, 8 H),
3
3
7.03 (d, J ) 5.5 Hz, 4 H), 6.79 (d, J ) 5.9 Hz, 8 H), 1.76 (s,
8 H), 1.35 (s, 24 H), 0.78 (s, 36 H). 13C NMR (125 MHz, THF,
25 °C): δ (ppm) ) 155.50 (arom q), 154.73 (arom q), 145.35
(arom q), 136.03 (arom q), 127.92 (arom CH), 127.83 (arom
CH), 126.22 (arom CH), 119.84 (arom q), 118.25 (arom CH),
117.30 (arom q), 57.74 (aliph q), 38.90 (aliph q), 33.02 (CH2),
32.31 ((CH3)2), 32.15 ((CH3)3). FD-MS: m/z (u e0-1) ) 1068.7
(100%, M+) (calcd:1069.5). FT-IR: ν ) 2951, 2901, 1599 (νCd
O), 1490, 1384, 1364, 1249, 1220, 1172, 1014, 879, 828, 579
cm-1. UV (CHCl3):
(16 019); 444 nm (18 452 L mol-1 cm-1). Anal. Calcd for
λmax(ꢀ) ) 359 (6834); 376 (8707); 422
C
76H92O4: C, 85.35; H, 8.67. Found: C, 85.36; H, 8.65.
3,9-(3,10)-Dib r om o-1,6,7,12-t e t r a k is[4-(1,1,3,3-t e t r a -
m eth ylbu tyl)p h en oxy]p er ylen e (10). A solution of 1,6,7,12-
tetrakis[4′-(1′′,1′′,3′′,3′′-tetramethylbutyl)phenoxy]perylene (9)
(5.7 g, 5.33 mmol) in DMF (700 mL) was heated to 60 °C. After
addition of NBS (3.5 g, 19.1 mmol) the solution was stirred at
60 °C for 3 h, with the progress of the reaction being monitored
by TLC. The solution was cooled to room temperature and
poured into a stirred mixture of water/concentrated HCl (10:
1). The product was extracted with dichloromethane, and the
organic layer was washed with water and dried over magne-
sium sulfate. After evaporation of the solvent under vacuum
the yellow solid was purified by column chromatography on
silica eluting with dichloromethane/n-hexane (1:2) (yield: 6.15
g, 94%).
10: mp 133-134 °C. 1H NMR (500 MHz, THF, 25 °C): δ
3
3
(ppm) ) 7.96 (d, J ) 2.4 Hz, 2 H), 7.29 (m, 10 H), 7.13 (d, J
3
) 2.4 Hz, 2 H), 6.82 (m, 8 H), 1.74 (d, J ) 4.6 Hz, 8 H), 1.34
(s, 24 H), 0.77 (tr, 3J ) 6.2 Hz, 36 H). 13C NMR (125 MHz,
C2D2Cl4, 393 K): δ (ppm) ) 127.47, 119.44, 103.06, 57.55,
38.55, 32.45, 32.03, 31.67.
P o ly [1,5,7,12-T e t r a k is {(1,1,3,3-t e t r a m e t h y lb u t y l)-
p h en oxy}p er ylen e-3,9(3,10)-d iyl] (3a ). A solution of bis-
(cyclooctadiene)nickel(0) (158 mg, 0.58 mmol), 2,2′-bipyridine
(90 mg, 0.58 mmol), and 1,5-cyclooctadiene (0.13 mL) in
dimethylformamide (2.5 mL) was prepared in a Schlenk tube
under glovebox conditions. The solution was heated to 80 °C
for 20 min under argon, and then a solution of 336 mg (0.27
mmol) of the dibromide 10 (336 mg, 0.27 mmol) in dry toluene
(5 mL) was added via syringe. The reaction mixture was stirred
for 3 days at 90 °C. Then bromobenzene (253 mg, 1.62 mmol)
and 158 mg (0.58 mmol) of bis(cyclooctadiene)nickel(0) (158
mg, 0.58 mmol) were added, and the solution was stirred for
another 24 h at 90 °C. After cooling to room temperature
toluene (80 mL) was added, and the organic phase was washed
with a 10% aqueous HCl solution (100 mL). The solvent was
removed under reduced pressure, and after dissolution of the
Ack n ow led gm en t. We thank Erik Reuther for his
assistance in the preparation of this manuscript and
BASF-AG, Ludwigshafen, for providing the tetrachlo-
roperylene tetracarboxylic acid dianhydride.
Refer en ces a n d Notes
(1) Bre´das, J . L.; Baughman, J . J . Chem. Phys. 1985, 83, 1316.
(2) Karaburnaliev, S.; Ghergel, L.; Koch, K.-H.; Baumgarten, M.
Chem. Phys. 1994, 189, 53.
(3) Koch, K.-H.; Mu¨llen, K. Chem. Ber. 1991, 124, 2091.

1582 Former et al.
Macromolecules, Vol. 35, No. 5, 2002
(4) Bohnen, A.; Koch, K. H.; Lu¨ttke, W.; Mu¨llen, K. Angew.
Chem., Int. Ed. Engl. 1990, 29, 525.
(5) Koch, K. H.; Fahnenstich, U.; Baumgarten, M.; Mu¨llen, K.
Synth. Met. 1991, 41-43, 1619.
(6) Quante, H.; Schlichting, P.; Rohr, U.; Geerts, Y.; Mu¨llen, K.
Macromol. Chem. Phys. 1996, 197, 4029.
(7) Schneider, M.; Mu¨llen, K. Chem. Mater. 2000, 12, 352.
(8) Brandrup, J .; Immergut, E. H.; Grulke, E. A. Polymer
Handbook, 4th ed.; J ohn Wiley and Sons: New York, 1999.
(9) Kovacic, P.; J ones, M. B. Chem. Rev. 1987, 87, 357.
(10) Houben-Weyl Oxidation; Georg Thieme Verlag: Stuttgart,
1993.
(11) Vanhee, S.; Rulkens, R.; Lehmann, U.; Rosenauer, C.;
Schulze, M.; Ko¨hler, W.; Wegner, G. Macromolecules 1996,
29, 5136.
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