Core-extended perylene tetracarboxdiimides: The homologous series of coronene tetracarboxdiimides

Article abstract of DOI:10.1021/ol201623f

Two novel coronenediimide (CDI) derivatives, CDI 2 and dinaphtho-CDI 4, were synthesized via straightforward synthetic routes completing the homologous series of coronene tetracarboxdiimides, which show remarkable optical properties with absorption wavele

Full text of DOI:10.1021/ol201623f

ORGANIC
LETTERS
2011
Vol. 13, No. 15
4148–4150
Core-Extended Perylene
Tetracarboxdiimides: The
Homologous Series of Coronene
Tetracarboxdiimides
€
Christian Lutke Eversloh, Chen Li,* and Klaus Mullen*
€
Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
lichen@mpip-mainz.mpg.de; muellen@mpip-mainz.mpg.de
Received June 16, 2011
ABSTRACT
Two novel coronenediimide (CDI) derivatives, CDI 2 and dinaphtho-CDI 4, were synthesized via straightforward synthetic routes completing the
homologous series of coronene tetracarboxdiimides, which show remarkable optical properties with absorption wavelengths ranging from 380 to
600 nm, high absorption coefficients, and high fluorescence quantum yields.
Coronene dyes, both the pure hydrocarbon derivatives
and coronene tetracarboxdiimides (CDIs), have been the
focus of research for many years. Thus various synthetic
routes to coronene and core-expanded analogs are
known,1 but most of them suffer from numerous reaction
steps and low yields.2 Furthermore only a few reactions are
known for the preparation of CDIs,3 which can be re-
garded as bay-extended perylene tetracarboxdiimides
(PDIs),4 and for this reason most syntheses start from
the latter. Particularly the enlargement of the π-system
along the short molecular axis of PDI (1) attracts huge
interest5 and offers access to various biological6 as well as
organic electronic applications7 such as light-emitting
diodes3c and field-effect transistors.8 Herein we present
the straightforward syntheses of two novel chromophores,
(6) (a) Franceschin, M.; Alvino, A.; Casagrande, V.; Mauriello, C.;
Pascucci, E.; Savino, M.; Ortaggi, G.; Bianco, A. Bioorg. Med. Chem.
2007, 15 (4), 1848–1858. (b) Franceschin, M.; Alvino, A.; Ortaggi, G.;
Bianco, A. Tetrahedron Lett. 2004, 45 (49), 9015–9020.
(1) van Dijk, J. T. M.; Hartwijk, A.; Bleeker, A. C.; Lugtenburg, J.;
Cornelisse, J. J. Org. Chem. 1996, 61 (3), 1136–1139.
€
(2) Vogtle, F. Reizvolle Moleku€le der Organischen Chemie; Teubner:
Stuttgart, 1989.
(7) (a) Zhan, X.; Facchetti, A.; Barlow, S.; Marks, T. J.; Ratner,
M. A.; Wasielewski, M. R.; Marder, S. R. Adv. Mater. 2011, 23 (2), 268–
€
(3) (a) Wurthner, F. Chem. Commun. 2004, 14, 1564–1579. (b)
Alibert-Fouet, S.; Seguy, I.; Bobo, J.-F.; Destruel, P.; Bock, H.
€
284. (b) Herrmann, A.; Mullen, K. Chem. Lett. 2006, 35 (9), 978–985. (c)
Chem.;Eur. J. 2007, 13 (6), 1746–1753. (c) Rohr, U.; Schlichting, P.;
€
Samorı, P.; Severin, N.; Simpson, C. D.; Mullen, K.; Rabe, J. P. J. Am.
´
€
€
€
Bohm, A.; Gross, M.; Meerholz, K.; Brauchle, C.; Mullen, K. Angew.
Chem. Soc. 2002, 124 (32), 9454–9457. (d) Pollard, A. J.; Perkins, E. W.;
Smith, N. A.; Saywell, A.; Goretzki, G.; Phillips, A. G.; Argent, S. P.;
Chem., Int. Ed. 1998, 37 (10), 1434–1437.
€
€
€
(4) Avlasevich, Y.; Li, C.; Mullen, K. J. Mater. Chem. 2010, 20 (19),
3814–3826.
Sachdev, H.; Muller, F.; Hufner, S.; Gsell, S.; Fischer, M.; Schreck, M.;
Osterwalder, J.; Greber, T.; Berner, S.; Champness, N. R.; Beton, P. H.
Angew. Chem., Int. Ed. 2010, 49 (10), 1794–1799.
(5) (a) Jiang, W.; Li, Y.; Yue, W.; Zhen, Y.; Qu, J.; Wang, Z. Org.
Lett. 2009, 12 (2), 228–231. (b) Qian, H.; Yue, W.; Zhen, Y.; Di Motta,
S.; Di Donato, E.; Negri, F.; Qu, J.; Xu, W.; Zhu, D.; Wang, Z. J. Org.
Chem. 2009, 74 (16), 6275–6282. (c) Yao, J. H.; Chi, C.; Wu, J.; Loh, K.-
P. Chem.;Eur. J. 2009, 15 (37), 9299–9302.
€
€
(8) (a) Nolde, F.; Pisula, W.; Muller, S.; Kohl, C.; Mullen, K. Chem.
Mater. 2006, 18 (16), 3715–3725. (b) An, Z.; Yu, J.; Domercq, B.; Jones,
S. C.; Barlow, S.; Kippelen, B.; Marder, S. R. J. Mater. Chem. 2009, 19
(37), 6688–6698.
r
10.1021/ol201623f
Published on Web 07/01/2011
2011 American Chemical Society

namely coronene tetracarboxdiimide 2 and dinaphthocor-
onene tetracarboxdiimide 4 (Scheme 1). In combination
with the already known dibenzo-CDI39 we are now able to
present a new homologous series of symmetrically ex-
tended coronene tetracarboxdiimides by a stepwise enlar-
gement of the perylene core.
Table 1. Optical and Electrochemical Properties According UV
and CV Measurement
λ
max/nm
λ
em/nm
ΔEopt
/
ELUMO/
eVb
Compound
PDI 1
(log ε)
(Φ)
eVa
458 (4.1)
489 (4.5)
525 (4.7)12
397 (4.4)
421 (4.7)
494 (4.2)
460 (4.5)
494 (4.8)13
496 (4.4)
530 (4.4)
573 (4.4)
540
2.00
2.46
À3.86
575
(0.98)12
498
Scheme 1. Synthesis of CDI 2 and Dinaphtho-CDI 4a
CDI 2
À3.62
534
(0.69)
505
(0.80)13
584
Dibenzo-CDI 3
2.42
2.07
À3.75
À3.84
Dinaphtho-CDI 4
(0.42)
a Optical band gap according UV/vis absorption (onset method).
b Energy level of lowest unoccupied molecular orbital according
cyclovoltammetry.
available 3-(trimethylsilyl)naphthyl-trifluormethane-sul-
fonate in a mixture of toluene and acetonitrile at reflux
furnished the desired product 4 in 46% yield.
a (a) DBU, toluene, 60 °C-reflux, 6À24 h; (b) PtCl2, toluene, 90 °C,
48 h; (c) Pd(dba)2, P(o-tol)3, CsF, toluene, CH3CN, reflux, 18 h.
Both synthetic routes start from the corresponding 1,7-
dibromoperylene tetracarboxdiimide 5 which usually con-
tains various amounts of the 1,6-isomer, but for symmetry
reasons even the mixture of isomers is suitable to form the
appropriate products. In the case of the formation of the
CDI 2 the dibromo-PDI 5 was coupled under Sonogashira
conditions with bis-(trimethylsilyl)-acetylene as the first
step to afford 6 in 74% yield. Unfortunately the second
step including the application of DBU (1,8-diazabicyclo-
[5.4.0]undec-7-ene) to cyclize the ethinyl-precursor 6 re-
sulting in 2 as already described for its alkyl substituted
congener was not successful in this case.10 Neither the
bis-(trimethylsilyl)-coronenediimide 2b nor the requested
CDI 2 itself could be obtained. Instead a PtCl2 catalyzed
carbocyclization11 of the trimethylsilylethinyl groups in
toluene proved to be the right choice to achieve 2 in a
reasonable yield, while the trimethylsilyl groups were
cleaved within this process.
Figure 1. Absorption (solid line) and emission spectrum (dashed
line, λex = 410 nm) of CDI 2 in toluene.
It is already known from the established CDIs and
dibenzo-CDIs that an extension of the core of perylene
tetracarboxdiimides in some cases induces a shift toshorter
wavelengths in their absorption spectra, which is in con-
trast to the extension along their long molecular axis.4
Nevertheless starting from CDI 2(λmax = 421 nm) (Figure 1)
leading to dibenzo-CDI 3 (λmax = 494 nm)9 and di-
naphtho-CDI 4 (λmax = 496, 530, 573 nm) (Figure 2), a
stepwise bathochromic shift can be observed for each
extension along the short molecular axis. It is noteworthy
at this point that the novel dinaphtho-CDI 4 on its own
shows a broad absorption from 450 to 600 nm and an
In contrast to the preparation of CDI 2, the synthesis
of dinaphtho-CDI 4 was carried out in one step according
to the analogous procedure for the synthesis of diben-
zo-CDI via o-(trimethylsilyl)phenyl triflate recently
described by us.9 It appeared in this case that using
the dibromo-PDI 5 together with the commercially
€
€
(9) Avlasevich, Y.; Muller, S.; Erk, P.; Mullen, K. Chem.;Eur. J.
2007, 13 (23), 6555–6561.
(10) Rohr, U.; Kohl, C.; Mullen, K.; van de Craats, A.; Warman, J. J.
€
€
Mater. Chem. 2001, 11 (7), 1789–1799.
(12) Rademacher, A.; Markle, S.; Langhals, H. Chem. Ber. 1982, 115
(8), 2927–2934.
ꢀ
(11) Storch, J.; Cermak, J.; Karban, J. Tetrahedron Lett. 2007, 48
(38), 6814–6816.
€
€
(13) Mullen, S.; Mullen, K. Chem. Commun. 2005, 32, 4045–4046.
Org. Lett., Vol. 13, No. 15, 2011
4149

Figure 3. Molecular orbitals of Dinaphtho-CDI 4. Abbrevia-
tions: (HOMO) highest occupied molecular orbital, (LUMO)
lowest unoccupied molecular orbital (Gaussian 03W, AM1).
Figure 2. Absorption (solid line) and emission spectrum (dashed
line, λex = 510 nm) of Dinaphtho-CDI 4 in toluene.
absorption coefficient of 22700 MÀ1 cmÀ1 giving the
substance a bright purple-red appearance. Furthermore
its absorption spectrum does not exhibit the typical per-
ylene vibronic fine structure, as this is observed for most
perylene and coronene tetracarboxdiimides. Instead it
shows an anthracene-like absorption behavior.14 An ex-
planation for this can be given from the respective frontier
orbital calculations (Gaussian 03W, AM1), which reveal
the influence of the anthracene HOMO on the electronic
structure of 4 (Figure 3). As expected, the absorption
spectrum of the coronene tetracarboxdiimide 2 resembles
that of the alkyl substituted CDI, which was already
described earlier.10 The small Stokes shifts of about 5À15
nm, which are typically observed for perylene and coro-
nene tetracarboxdiimides, lead to fluorescence maxima of
498 and 534 nm with a quantum yield of 69% for CDI 2
and an emission at 584 nm (Φ = 42%) for the dinaphtho-
CDI 4 (Table 1).
not only by the extension at their long molecular axis but
also at their short axis. Additionally, the coronene tetra-
carboxdiimides of the presented series show versatile ab-
sorption and emission behavior with high absorption
coefficients and fluorescence quantum yields. Especially
the dinaphtho-CDI 4 offers interesting optical properties,
as its absorption spectrum covers a broad range of the
visible light. Additionally the similarity of the LUMO
energy levels of 4 and the established PDI 17 makes
compound 4 a promising dye for organic photovoltaics.
In analogy to known perylene dyes15 one can furthermore
envision its use as a red emitting dye in organic light
emitting diodes due to its strong fluorescence at 584 nm.
Finally the reaction leading to dinaphtho-CDI 4 opens the
possibility to achieve even larger extended coronene diimides.
Acknowledgment. We gratefully acknowledge financial
€
support from the Bundesministerium fur Bildung und
Forschung (BMBF) and BASF SE.
In summary we presented the syntheses of CDI 2 and
dinaphtho-CDI 4 as two novel derivatives in the series of
coronene tetracarboxdiimides. Both compounds are avail-
able via short and straightforward routes in reasonable
overall yields starting from the well-known dibromo-PDI
5. With this knowledge we are now able to tune the
properties of perylene and coronene tetracarboxdiimides
Supporting Information Available. Full experimental
details and characterization data. This material is avail-
able free of charge via the Internet at http://pubs.acs.org.
(15) (a) Ego, C.; Marsitzky, D.; Becker, S.; Zhang, J.; Grimsdale,
€
A. C.; Mullen, K.; MacKenzie, J. D.; Silva, C.; Friend, R. H. J. Am.
Chem. Soc. 2003, 125 (2), 437–443. (b) Tan, W.; Li, X.; Zhang, J.; Tian,
H. Dyes Pigm. 2011, 89 (3), 260–265.
(14) Jones, R. N. Chem. Rev. 1947, 41, 353–371.
4150
Org. Lett., Vol. 13, No. 15, 2011