Core-tetrasubstituted naphthalene diimides by stille cross-coupling reactions and characterization of their optical and redox properties

Article abstract of DOI:10.1055/s-0029-1216785

The palladium-catalyzed cross-coupling reaction of 2,3,6,7- tetrabromonaphthalene diimide with various aryl- and alkynylstannanes afforded a series of hitherto unknown tetraaryl- and tetraethynyl-substituted naphthalene diimides (NDIs). UV/Vis spectroscop

Full text of DOI:10.1055/s-0029-1216785

PAPER
1841
Core-Tetrasubstituted Naphthalene Diimides by Stille Cross-Coupling
Reactions and Characterization of Their Optical and Redox Properties
Aryl- and
Alka
b
ubstituted
N
a
phthale
n
ne
D
iimides-Lucian Suraru, Frank Würthner*
Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
Fax +49(931)3184756; E-mail: wuerthner@chemie.uni-wuerzburg.de
Received 18 November 2008; revised 26 January 2009
stitution of 2,3,6,7-tetrabromonaphthalene diimides,
which are accessible by imidization of 2,3,6,7-tetrabro-
monaphthalene dianhydride,14,15 with alkoxy, alkylamino,
and alkylthio nucleophiles afforded the corresponding
Abstract: The palladium-catalyzed cross-coupling reaction of
2,3,6,7-tetrabromonaphthalene diimide with various aryl- and alky-
nylstannanes afforded a series of hitherto unknown tetraaryl- and
tetraethynyl-substituted naphthalene diimides (NDIs). UV/Vis
spectroscopic studies revealed that the absorption maxima of ethy- core-tetrasubstituted NDI dyes with interesting electronic
properties.14 Very recently, palladium-catalyzed cross-
nyl-substituted NDIs are significantly bathochromically shifted
compared to those of unsubstituted and tetraaryl-substituted NDIs.
coupling reactions with 2,6-dibromonaphthalene diimides
Cyclic voltammetry investigations showed that ethynyl substituents
have been performed to afford 2,6-dicyano, diaryl, and di-
shift the reduction potentials of NDIs anodically, thus these NDI de-
ethynyl NDI derivatives,16a,b and thiophene-based conju-
rivatives are interesting candidates for air-stable n-channel organic
gated polymers of disubstituted NDIs.16c,d However, to
our knowledge such a cross-coupling reaction of 2,3,6,7-
tetrabromonaphthalene diimides has not been reported so
far and except a tetrathiophene-NDI derivative that was
prepared by Stille reaction of tetrabromonaphthalene di-
field-effect transistors.
Key words: chromophores, arylenes, cross-coupling, Stille reac-
tion, catalysis
anhydride and subsequent imidization,17 no further exam-
Naphthalene diimides (NDIs) are an important class of
ples of tetraaryl- or tetraethynyl-substituted NDIs are
chromophores with favorable properties for applications
known.18
as organic materials and in functional supramolecular sys-
tems.1 For example, NDIs have been used as n-type semi-
conductors in organic field-effect transistors (OFETs),2 as
electron-acceptor units in photoinduced charge separation
arrays,3 light-harvesting chromophores of synthetic rod
antennae,4 and light-absorbing charge transport units in
self-assembled systems for photoproduction of transmem-
brane proton gradient.5 In recent years, chemosensors6,7
and supramolecular switches8 have been developed based
on NDI derivatives. Furthermore, extended supramolecu-
lar architectures such as helical nanotubes9 and synthetic
ion channels10a,b and zipper assemblies10c,d have been con-
structed using naphthalene diimides.
Here we report on the palladium-catalyzed Stille reactions
of 2,3,6,7-tetrabromonaphthalene diimide 1 with elec-
tron-rich, electron-poor and neutral organostannanes to
afford the new tetraaryl- and tetraethynylnaphthalene di-
imides 2a–c and 3a,b (Scheme 1). The starting compound
2,3,6,7-tetrabromonaphthalene diimide 1 was prepared by
imidization of 2,3,6,7-tetrabromonaphthalene dianhy-
dride with n-octylamine according to the literature meth-
od.15
Stille cross-coupling reaction of tetrabrominated NDI 1
with 6.6 equivalents of tributylphenylstannane in the pres-
ence of Pd(PPh3)4 as catalyst in toluene afforded the tet-
raphenyl-substituted NDI 2a in 54% yield. To explore
whether electron-rich or electron-poor aryl groups can
also be introduced at the naphthalene core by this method,
tributyl(4-methoxyphenyl)stannane and tributyl(4-cy-
anophenyl)stannane were reacted with NDI 1 using
Pd(dba)2 and Ph3As as catalysts. Indeed, the correspond-
ing tetraaryl-substituted NDIs 2b and 2c were obtained in
38% and 47% yield, respectively. It is noteworthy that
with Pd(PPh3)4 as catalyst similar results were obtained as
for Pd(dba)2 and Ph3As. The latter combination, however,
is easier to handle under ambient conditions. As next, we
have investigated the cross-coupling of NDI 1 with ethy-
nylstannanes under Stille conditions. Pleasingly, the reac-
tion of NDI 1 with tributyl(phenylethynyl)stannane and
tributyl[(trimethylsilyl)ethynyl]stannane in the presence
of Pd(PPh3)4 catalyst provided the very first examples of
tetraethynyl-substituted naphthalene diimides 3a and 3b
in 25% and 45% yield, respectively. It is noteworthy that,
The electronic properties of naphthalene diimides are de-
cisive for most of the applications mentioned above and
they can be tuned by introducing substituents at the naph-
thalene core.11 Thus, numerous core-substituted NDIs
have previously been reported. Core-disubstituted NDIs
were made accessible from the 2,6-dichloro- and 2,6-di-
bromonaphthalene dianhydride by imidization with
amines, followed by subsequent exchange of halogen at-
oms with nitrogen, oxygen, sulfur, and selenium nucleo-
philes.11,12 Core-trisubstituted naphthalene diimides
containing triamine or monoalkoxy and diamino groups
were obtained by the reaction of 2,6-dichloronaphthalene
diimide with ethylenediamine or by successive reactions
with ethylenediamine and an alcohol.13 Nucleophilic sub-
SYNTHESIS 2009, No. 11, pp 1841–1845
x
x.
x
x
.
2
0
0
9
Advanced online publication: 30.04.2009
DOI: 10.1055/s-0029-1216785; Art ID: T20008SS
© Georg Thieme Verlag Stuttgart · New York

1842
S.-L. Suraru, F. Würthner
PAPER
C8H17
C8H17
N
C8H17
N
R
O
N
O
R
R
O
O
O
O
O
O
O
O
R
R
R
R
Br
Br
Br
Br
i–iii
iv, v
38–54%
25–45%
R
O
N
O
N
N
C8H17
C8H17
C8H17
2
1
3
a: R = H; b: R = OMe; c: R = CN
a: R = Ph; b: R = SiMe3
Scheme 1 Synthesis of tetraaryl- and tetraethynyl-substituted naphthalene diimides 2a–c and 3a,b by Stille coupling reactions under argon
atmosphere. Reagents and conditions: (i) tributylphenylstannane, Pd(PPh3)4, toluene, reflux, 70 h, yield 2a: 54%; (ii) tributyl(4-methoxyphe-
nyl)stannane, Pd(dba)2, Ph3As, toluene, reflux, 19 h, yield 2b: 38%; (iii) tributyl(4-cyanophenyl)stannane, Pd(dba)2, Ph3As, toluene, reflux,
28 h, yield 2c: 47%; (iv) tributyl(phenylethynyl)stannane, Pd(PPh3)4, toluene, reflux, 21 h, yield 3a: 25%; (v) tributyl[(trimethylsilyl)ethy-
nyl]stannane, Pd(PPh3)4, toluene, reflux, 24 h, yield 3b: 45%.
although copper(I)-cocatalyzed Sonogashira reaction of
2,6-dibromo NDI had been previously applied to prepare
the respective diethynyl-substituted NDIs,16b the reactions
of 2,3,6,7-tetrabromo NDI 1 with phenylacetylene and tri-
methylsilylacetylene under Sonogashira conditions led to
a complex mixture and only little amounts (4–8%) of the
desired cross-coupling products could be obtained.
The new 2,3,6,7-tetrasubstituted NDIs 2a–c and 3a,b
1
were characterized by H and 13C NMR spectra, UV/Vis
spectroscopy, high-resolution mass spectrometry, and
elemental analysis.
The optical properties of the NDIs 2a–c and 3a,b were
studied by UV/Vis spectroscopy in dichloromethane. The
phenyl- and 4-cyanophenyl-substituted NDIs 2a and 2c
are yellow nonfluorescent compounds, exhibiting absorp-
tion maxima at 360 and 377 nm, and at 359 and 379 nm,
respectively (Figure 1, a). The position and vibronic struc-
ture is very similar to that of the core-unsubstituted NDI-
C8 with an n-octyl substituent at the imide position (359
and 380 nm),11c,15 indicating a limited conjugation of the
phenyl substituents with the naphthalene core. Interest-
ingly, the red NDI 2b bearing four 4-methoxyphenyl
Figure 1 (a) UV/Vis absorption spectra of NDIs 2a (pink line), 2b
(red line), 2c (blue line) and, for comparison, of the core-unsubstitu-
ted NDI-C8 (black line); and (b) of 3a (dashed line) and 3b (solid line)
groups at the naphthalene core exhibits an additional
broad band with an absorption maximum at 480 nm of
weak intensity. This band can be attributed to a charge-
transfer transition as previously reported for some di- and
tetrasubstituted NDIs.11a,16b The broadening of this band
(as well as the tailing of the absorption bands of 2a and 2c)
is attributed to the presence of noncoplanar conformations
evoked by steric constraints that distort the chromophore
(in particular around the phenyl–naphthalene single
bonds). Compared with the aryl-substituted NDIs 2a–c,
ethynyl-substituted NDIs 3a and 3b exhibit significantly
red-shifted well-defined absorption bands (Figure 1, b).
This red-shift is the consequence of an extended p-conju-
gation in the absence of sterical encumbering. For NDI
3a, a weak fluorescence with a quantum yield of 0.6% was
observed. The remaining NDI dyes are nonfluorescent.
are shown in Figure 2 as representative examples. All of
these NDIs show two well separated reversible reduction
waves, respectively. Comparing with the reduction poten-
tials of the unsubstituted NDI-C8 (–1.10 and –1.51 V vs.
Fc/Fc+),11c the reduction waves of the phenyl-substituted
NDI 2a (–1.19 and –1.66 V vs. Fc/Fc+) and the methoxy-
phenyl-substituted NDI 2b (–1.26 and –1.72 V vs. Fc/Fc+)
are shifted to more negative values, while NDI 2c contain-
ing electron-withdrawing 4-cyanophenyl groups displays
significantly anodically shifted reduction waves (–0.92
and –1.46 V vs. Fc/Fc+). Likewise the phenylethynyl-sub-
stituted NDI 3a (–0.93 and –1.30 V vs. Fc/Fc+) is more
easily reducible than the unsubstituted NDI-C8 and the
phenyl-substituted NDI 2a. This can be attributed to an
extension of the LUMO orbitals by four ethynyl substitu-
ents.16b For NDI 3b (–0.97 and –1.35 V vs. Fc/Fc+) similar
The redox properties of the NDIs 2a–c and 3a,b were
studied by cyclic voltammetry in dichloromethane with
ferrocene as internal standard. The results are summarized
in Table 1 and cyclic voltammograms of NDIs 2a and 3a
Synthesis 2009, No. 11, 1841–1845 © Thieme Stuttgart · New York

PAPER
Aryl- and Alkynyl-Tetrasubstituted Naphthalene Diimides
1843
surements were performed in a conventional quartz cell (light pass
10 mm) on a PerkinElmer Lambda 950 spectrometer. Emission
spectra were measured in a conventional rectangular quartz cell
(10 × 10 × 40 mm) on a PTI QM4-2003 fluorescence spectrometer
and are corrected against photomultiplier and lamp intensity. A long
wavelength range emission-corrected photomultiplier R928 was
used. Fluorescence quantum yields were determined under dilute
conditions in CH2Cl2 (<10–6 M) versus N,N¢-(2,6-diisopropylphe-
nyl)-1,6,7,12-tetraphenoxyperylene-3,4:9,10-tetracarboxylic acid
bisimide (Ffl = 0.96 in CHCl3).25 For cyclic voltammetry, a stan-
dard commercial electrochemical analyzer (EC epsilon; BAS In-
struments, UK) with a three electrode single-compartment cell was
used. CH2Cl2 (HPLC grade) was dried over CaH2 under argon and
degassed before using. The supporting electrolyte tetrabutylammo-
nium hexafluorophosphate (TBAHFP) was prepared according to
the literature,26 and recrystallized from EtOH–H2O. The measure-
values are observed. Within the available potential range
in dichloromethane only for NDI 2b an irreversible oxida-
tion could be observed at around 1.16 V.
Table 1 Half-Wave Reduction Potentials of Core-Tetrasubstituted
NDIs 2a–c and 3a,b and Reference Compound NDI-C8 in Volt (V)
vs. Fc/Fc+
E1/2
2a
2b
2c
3a
3b
NDI-C8
–1.10
X/X–
–1.19
–1.26
–1.72
–0.92
–1.46
–0.93
–1.30
–0.97
–1.35
X–/X2– –1.66
–1.51
ments were carried out in CH2Cl2 at a concentration of about 10–4
M
with ferrocene (Fc) as internal standard for the calibration of the po-
tential. Ag/AgCl reference electrode was used. A Pt disc and a Pt
wire were used as working and auxiliary electrodes, respectively.
Attention! Because of their high toxicity, organostannanes must be
handled with caution!
N,N¢-Di-(n-octyl)-2,3,6,7-tetraphenyl-1,4,5,8-naphthalenetetra-
carboxylic Acid Diimide (2a)
Compound
1
(210 mg, 0.26 mmol), tributylphenylstannane
(635 mg, 1.73 mmol), and Pd(PPh3)4 (14.0 mg, 12.1 mmol) were
combined in toluene (10 mL) and heated under reflux in an argon
atmosphere for 70 h. The solvent was removed under reduced pres-
sure and the residue was purified by column chromatography (n-
hexane–THF, 96:4). A yellow solid was obtained (111 mg, 54%);
Figure 2 Cyclovoltammograms for NDIs 2a and 3a
In conclusion, our present study has revealed that the mp 198–200 °C.
1H NMR (400 MHz, CDCl3): d = 0.84 (t, J = 7.0 Hz, 6 H), 1.12–
3
Stille cross-coupling reaction is a convenient method for
the synthesis of tetraaryl- and tetraethynyl-substituted
naphthalene diimides which has not previously been ap-
plied to tetrabromonaphthalene diimides. In aryl-substi-
tuted NDIs the p-conjugation between the NDI core and
the four substituents is apparently restricted due to steric
constraints, while in ethynyl-substituted NDI extended p-
conjugation is given as reflected in bathochromically
shifted absorption maxima and lower (less negative) re-
duction potentials of latter derivatives. Because of their
electron-deficient character, these tetraethynyl NDIs
should be interesting n-type semiconductors for air-stable
n-channel organic field-effect transistors.19,20
1.29 (m, 20 H), 1.30–1.41 (m, 4 H), 3.86 (t, 3J = 7.6 Hz, 4 H), 6.86–
6.93 (m, 8 H), 7.14–7.23 (m, 12 H).
13C NMR (101 MHz, CDCl3): d = 14.3, 22.8, 27.2, 28.2, 29.4, 29.5,
31.9, 41.2, 124.2, 126.9, 127.2, 127.7, 128.8, 139.4, 149.1, 162.2.
HRMS (ESI, +): m/z [M + H]+ calcd for C54H55N2O4: 795.4156;
found: 795.4156.
UV/Vis (CH2Cl2): lmax (e) = 253 (62500), 360 (15900), 377 nm
(16300 M–1 cm–1).
CV (CH2Cl2, 0.1 M TBAHFP, vs. Fc/Fc+): Ered (X–/X2–) = –1.66 V,
E
red (X/X–) = –1.19 V.
Anal. Calcd for C54H54N2O4: C, 81.58; H, 6.85; N, 3.52. Found: C,
81.36; H, 6.99; N, 3.51.
N,N¢-Di-(n-octyl)-2,3,6,7-tetrakis(4-methoxyphenyl)-1,4,5,8-
naphthalenetetracarboxylic Acid Diimide (2b)
The starting compound tetrabromonaphthalene diimide 1 was pre-
pared according to the literature.15 Tributylphenylstannane was ob-
Compound
1 (108 mg, 0.134 mmol), tributyl(4-methoxyphe-
tained
from
commercial
sources.
Tributyl(4-
methoxyphenyl)stannane,21
tributyl(4-cyanophenyl)stannane,22
nyl)stannane (384 mg, 0.967 mmol), Pd(dba)2 (7.90 mg,
13.7 mmol), and Ph3As (8.30 mg, 27.1 mmol) were combined in tol-
uene (10 mL) and heated under reflux in an argon atmosphere for
19 h. The solvent was removed under reduced pressure and the res-
idue was purified by column chromatography (CH2Cl2). An orange
solid was obtained (46.8 mg, 38%); mp 229–230 °C.
tributyl(phenylethynyl)stannane and tributyl[(trimethylsilyl)ethy-
nyl]stannane23 were prepared as described in the literature. All other
reagents and solvents were obtained from commercial suppliers and
purified and dried according to standard procedures.24 Column
chromatography was performed on silica gel (Merck Silica 60, par-
ticle size 0.040–0.063 mm). Solvents for spectroscopic studies were
of spectroscopic grade and used as received. Elemental analyses
were performed on a CHNS 932 analyzer (Leco Instruments Gm-
3
1H NMR (400 MHz, CDCl3): d = 0.85 (t, J = 7.0 Hz, 6 H), 1.14–
1.43 (m, 20 H), 1.43–1.51 (m, 4 H), 3.78 (s, 12 H), 3.88 (t,
3J = 7.5 Hz, 4 H), 6.71–6.81 (m, 16 H).
1
bH, Mönchengladbach, Germany). H and 13C NMR spectra were
13C NMR (151 MHz, CDCl3): d = 14.3, 22.8, 27.2, 28.3, 29.5, 29.6,
32.0, 41.2, 55.2, 113.4, 124.3, 127.0, 130.0, 131.8, 149.1, 158.4,
162.6.
HRMS (ESI, +): m/z [M + H]+ calcd for C58H63N2O8: 915.4579;
found: 915.4579.
recorded in CDCl3 on a Bruker Avance 400 or on a Bruker DMX
600 spectrometer. Residual undeuterated solvent was used as inter-
nal standard (7.26 ppm for 1H and 77.23 ppm for 13C spectra). High-
resolution ESI-TOF mass spectrometry was carried out on a mi-
croTOF focus instrument (Bruker Daltronik GmbH). UV/Vis mea-
Synthesis 2009, No. 11, 1841–1845 © Thieme Stuttgart · New York

1844
S.-L. Suraru, F. Würthner
PAPER
UV/Vis (CH2Cl2): lmax (e) = 249 (68800), 358 (17200),
7.61 mmol) were combined in toluene (9 mL) and heated under re-
flux in an argon atmosphere for 24 h. The solvent was removed un-
der reduced pressure and the residue was purified by column
chromatography (n-hexane–THF, 96:4). A yellow solid was ob-
tained (65.0 mg, 45%); mp 207–209 °C.
1H NMR (400 MHz, CDCl3): d = 0.39 (s, 36 H), 0.88 (t,
3J = 7.1 Hz, 6 H), 1.25–1.70 (m, 20 H), 1.70–1.78 (m, 4 H), 4.18 (t,
3J = 7.6 Hz, 4 H).
376 (18000), 480 nm (6200 M–1 cm–1).
CV (CH2Cl2, 0.1 M TBAHFP, vs. Fc/Fc+): Ered (X–/X2–) = –1.72 V,
E
red (X/X–) = –1.26 V.
Anal. Calcd for C58H62N2O8: C, 76.12; H, 6.83; N, 3.06. Found: C,
75.60; H, 6.76; N, 3.17.
N,N¢-Di-(n-octyl)-2,3,6,7-tetrakis(4-cyanophenyl)-1,4,5,8-naph-
thalenetetracarboxylic Acid Diimide (2c)
13C NMR (101 MHz, CDCl3): d = 0.1, 14.3, 22.9, 27.3, 28.0, 29.38,
Compound 1 (111 mg, 0.138 mmol), tributyl(4-cyanophenyl)stan-
nane (394 mg, 1.00 mmol), Pd(dba)2 (8.10 mg, 14.0 mmol), and
Ph3As (9.00 mg, 29.4 mmol) were combined in toluene (14 mL) and
heated under reflux in an argon atmosphere for 28 h. The solvent
was removed under reduced pressure and the residue was purified
by column chromatography (CH2Cl2). A yellow solid was obtained
(58.5 mg, 47%); mp 350–352 °C.
29.42, 32.1, 42.4, 101.9, 116.0, 125.3, 126.8, 130.7, 160.6.
HRMS (ESI, +): m/z [M + H]+ calcd for C50H71N2O4Si4: 875.4485;
found: 875.4482.
UV/Vis (CH2Cl2): lmax (e) = 319 (140100), 455 (20100), 485 nm
(44000 M–1 cm–1).
CV (CH2Cl2, 0.1 M TBAHFP, vs. Fc/Fc+): Ered (X–/X2–) = –1.35 V,
Ered (X/X–) = –0.97 V.
3
1H NMR (400 MHz, CDCl3): d = 0.85 (t, J = 7.0 Hz, 6 H), 1.13–
1.29 (m, 20 H), 1.36–1.49 (m, 4 H), 3.82 (t, 3J = 7.6 Hz, 4 H), 6.97–
Anal. Calcd for C50H70N2O4Si4: C, 68.60; H, 8.06; N, 3.20. Found:
C, 68.35; H, 8.25; N, 3.18.
7.02 (m, 8 H), 7.50–7.55 (m, 8 H).
13C NMR (101 MHz, CDCl3): d = 14.3, 22.8, 27.1, 28.0, 29.36,
29.37, 31.9, 41.6, 111.8, 118.5, 124.3, 127.7, 129.2, 131.9, 143.5,
147.0, 161.3.
Acknowledgment
HRMS (ESI, +): m/z [M + Na]+ calcd for C58H50N6O4 + Na:
917.3785; found: 917.3780.
We thank Ms. Ana-Maria Krause for the cyclic voltammetry mea-
surements, and the BMBF for financial support within the program
‘Organische Photovoltaik’.
UV/Vis (CH2Cl2): lmax (e) = 257 (116700), 359 (18200), 379 nm
(19400 M–1 cm–1).
CV (CH2Cl2, 0.1 M TBAHFP, vs. Fc/Fc+): Ered (X–/X2–) = –1.46 V,
E
References
red (X/X–) = –0.92 V.
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77.60; H, 5.68; N, 9.31.
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N,N¢-Di-(n-octyl)-2,3,6,7-tetrakis(phenylethynyl)-1,4,5,8-naph-
thalenetetracarboxylic Acid Diimide (3a)
Compound 1 (86.1 mg, 0.107 mmol), tributyl(phenylethynyl)stan-
nane (278 mg, 0.710 mmol), and Pd(PPh3)4 (7.00 mg, 6.06 mmol)
were combined in toluene (10 mL) and heated under reflux in an ar-
gon atmosphere for 21 h. The solvent was removed under reduced
pressure and the residue was purified by column chromatography
(CH2Cl2–n-pentane, 7:3). A red solid was obtained (24.3 mg, 25%);
mp 315–316 °C.
3
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1H NMR (400 MHz, CDCl3): d = 0.88 (t, J = 7.1 Hz, 6 H), 1.25–
1.49 (m, 20 H), 1.77–1.90 (m, 4 H), 4.26 (t, 3J = 7.7 Hz, 4 H), 7.33–
7.45 (m, 12 H), 7.71–7.76 (m, 8 H).
13C NMR (151 MHz, CDCl3, 40 °C): d = 14.1, 22.7, 27.2, 28.0,
29.28, 29.34, 32.0, 53.4, 88.9, 108.0, 123.1, 125.4, 125.6, 128.5,
129.6, 130.9, 132.6, 160.1.
HRMS (ESI, –): m/z [M]– calcd for C62H54N2O4: 890.4089; found:
890.4090.
(5) Bhosale, S.; Sisson, A. L.; Talukdar, P.; Fürstenberg, A.;
Banerji, N.; Vauthey, E.; Bollot, G.; Mareda, J.; Röger, C.;
Würthner, F.; Sakai, N.; Matile, S. Science 2006, 313, 84.
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UV/Vis (CH2Cl2): lmax (e) = 348 (65200), 535 nm (32600 M–1 cm–1).
Fluorescence (CH2Cl2, lex = 490 nm): lmax = 560 nm.
Fluorescence quantum yield (CH2Cl2): Ffl = 0.6%.
CV (CH2Cl2, 0.1 M TBAHFP, vs. Fc/Fc+): Ered (X–/X2–) = –1.30 V,
Ered (X/X–) = –0.93 V.
Anal. Calcd for C62H54N2O4: C, 83.57; H, 6.11; N, 3.14. Found: C,
83.29; H, 6.16; N, 3.40.
N,N¢-Di-(n-octyl)-2,3,6,7-tetrakis[(trimethylsilyl)ethynyl]-
1,4,5,8-naphthalenetetracarboxylic Acid Diimide (3b)
Compound 1 (130 mg, 0.161 mmol), tributyl[(trimethylsilyl)ethy-
nyl]stannane (600 mg, 1.55 mmol), and Pd(PPh3)4 (8.80 mg,
Synthesis 2009, No. 11, 1841–1845 © Thieme Stuttgart · New York

PAPER
Aryl- and Alkynyl-Tetrasubstituted Naphthalene Diimides
1845
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Synthesis 2009, No. 11, 1841–1845 © Thieme Stuttgart · New York