Regioselective functionalization of core-persubstituted perylene diimides

Article abstract of DOI:10.1002/chem.201400397

Regioselective functionalization of core per-substituted perylene diimides has been achieved efficiently based on a new versatile building block, named tetrabromotetrachloro-perylene-3,4:9,10-tetracarboxylic acid dianhydride (Br₄Cl₄-PTCDA), which affords a series of novel chromophores with impressive optoelectronic properties. Direct palladium-catalyzed fourfold intramolecular ring fusion affords successfully unique propeller-shaped biscarbazole[2,3-b]carbazole diimides with six annulated rings. Organic electronics: A series of novel chromophores were afforded by regioselective functionalization of core per-substituted perylene diimides (PDIs) (see scheme). Furthermore, new carbazole diimide derivatives with an extended π-conjugated system were synthesized by direct palladium-catalyzed intramolecular ring fusion.

Full text of DOI:10.1002/chem.201400397

DOI: 10.1002/chem.201400397
Communication
&
Materials Chemistry
Regioselective Functionalization of Core-Persubstituted Perylene
Diimides
Wan Yue,[a] Wei Jiang,*[a] Marcus Bçckmann,[b] Nikos L. Doltsinis,[b] and Zhaohui Wang*[a]
cient building blocks, not to mention the regioselective func-
Abstract: Regioselective functionalization of core per-sub-
tionalization of octa-substituted PDIs so far.
stituted perylene diimides has been achieved efficiently
We are highly enthusiastic about the design and synthesis of
based on a new versatile building block, named tetrabro-
novel electron-deficient conjugated systems based on rylene
motetrachloro-perylene-3,4:9,10-tetracarboxylic acid di-
diimides. Recently, we reported the facile homocoupling and
anhydride (Br4Cl4-PTCDA), which affords a series of novel
cross-coupling of PDIs and naphthalene diimides (NDIs) toward
chromophores with impressive optoelectronic properties.
fully conjugated rylene arrays by an Ullmann reaction, Stille re-
Direct palladium-catalyzed fourfold intramolecular ring
action, and CÀH transformation.[6] Very lately, a series of non-
fusion affords successfully unique propeller-shaped
bay-region cyano-substituted tetrachloro-perylene diimides
biscarbazole[2,3-b]carbazole diimides with six annulated
from BrxCl4-PDIs (x=1,2,3,4) with linearly correlated LUMO
rings.
levels have been developed by our group.[7] Herein, these de-
velopments have inspired us to design and synthesize a series
of core-persubstituted PDIs by a facile regioselective function-
The design and synthesis of high-performance electron-defi-
cient conjugated molecules is highly desirable due to the
urgent demand for effective electron-transporting materials
and functional components in organic electronics.[1] Perylene
diimides (PDIs, Figure 1) are a fascinating group of
candidates, which received considerable interest as
a result of their most promising application in n-type
organic field effect transistors, light-emitting diodes,
and solar cells.[2] To date, the classical modifications
of PDIs are focused on the bay-region (1, 6, 7, 12-po-
sitions) via halogen atoms and subsequent transfor-
mation to gain enormously valuable derivatives to
comply with various applications.[3] Only recently, has
functionalization on non-bay regions (2, 5, 8, 11-posi-
tions) been available by direct alkylation, arylation,
and borylation through metal-catalyzed CÀH bond
cleavage.[4] The first perchloro-substituted PDIs
(Cl8-PTCDI) are also reported as high-performance
alization from a simple and versatile building block, named tet-
rabromotetrachloro-perylene-3,4:9,10-tetracarboxylic acid di-
anhydride (5, Br4Cl4-PTCDA). In general, the accessibility of
these non-bay positions firstly allows us to functionalize the ar-
n-channel materials.[5] However, the number of the
examples of non-bay region functionlization PDIs is
still very limited due to a lack of a simple and effi-
Figure 1. Perylene diimides (PDIs, 1), 1,6,7,12-tetrachloro-2,5,8,11-tetrasubstituted pery-
lene diimides (X4Cl4-PDIs, 2), and biscarbazolo[2,3-b]carbazole diimides (3), R=alkyl and
aryl groups.
omatic cores regioselectively (2, Figure 1) to tune the optoelec-
tronic properties, in particular, higher electron affinities, facili-
tating electron injection. Furthermore, the retaining of the
chlorine atoms in the bay region renders the possibility for fur-
ther extension of the conjugated systems. Accordingly, direct
palladium-catalyzed intramolecular ring fusion affords propel-
ler-shaped biscarbazolo[2,3-b]carbazole diimides with six annu-
lated rings (3, Figure 1).
The key building block, Br4Cl4-PTCDA (5, Scheme 1) was pre-
pared by bromination of easily available tetrachloroperylene
dianhydride 4 with 2.5 equivalents dibromoisocyanuric acid in
an excellent yield. Suitable block-shaped single crystals for
[a] Dr. W. Yue, Dr. W. Jiang, Prof. Z. Wang
Beijing National Laboratory for Molecular Sciences
Institute of Chemistry, Chinese Academy of Sciences
Beijing, 100190 (P. R. China)
Fax: (+86)10-62653617
E-mail: jiangwei@iccas.ac.cn
wangzhaohui@iccas.ac.cn
[b] Dr. M. Bçckmann, Prof. N. L. Doltsinis
Institute for Solid State Theory
University of Mꢀnster
Wilhelm-Klemm-Str. 10, 48149 Mꢀnster (Germany)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201400397.
Chem. Eur. J. 2014, 20, 1 – 6
1
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Communication
Fluorine atoms could be intro-
duced into the non-bay regions
by nucleophilic halogen ex-
change of bromine atoms selec-
tively with potassium fluoride in
the presence of [18]crown-6 in
sulfolane to produce tetrachloro-
tetrafluoro-PDI (Cl4F4-PDI, 7).[9]
Reaction of compound 6 with
zinc cyanide and copper bro-
mide (or only CuCN) in refluxed
DMF can afford tetrachlorotetra-
cyano-PDI (Cl4CN4-PDI, 8) in
a good yield without metal cata-
lyst. The introduction of elec-
tron-deficient groups like fluoro
(7) and cyano (8) would have
a
strong influence on their
charge-transport properties,[10,3h]
particularly by decreasing the
LUMO levels to achieve air stabil-
ity of the semiconductors. Tetra-
chlorotetrathio-substituted PDI 9
can be smoothly obtained by
nucleophilic substitution with
thiophenol in the presence of
potassium carbonate as the base
in chloroform. Similarly, all four
bromine atoms of molecule 6
could be replaced by using
amine as a nucleophile, which
results in the corresponding tet-
rachlorotetraamino-functional-
ized PDIs 10a and 10c in an
almost quantitative yield;[11] this
Scheme 1. a) DBI, 50% oleum, 508C, 95%; b) n-octylamine or 2,6-diisopropylaniline, acetic acid, reflux, 6a (47%)
and 6b (30%); c) potassium fluoride, 18-crown-6, sulfolane, 1608C, 30%; d) zinc cyanide and copper bromide
DMF, reflux, 64%; e) thiophenol, K2CO3, CHCl3, reflux, 90%; f) 3,5-dimethylaniline or aniline, 1208C, 10a (93%), 10b same nucleophilic substitution
(85%) and 10c (92%). DBI=dibromoisocyanuric acid.
method could also be success-
fully extended to aryl-substituted
PDIs 10b. This incorporation of
the electron-donating thiophene
X-ray structure analysis were obtained by slow evaporation of
the mixture of dichloromethane and methanol solution at
room temperature, which further determines the molecular
structure of the Br4Cl4-PTCDA. The crystal structure of com-
pound 5 shows a twisted perylene backbone with a dihedral
angle of 56.758 between the C(7), C(8), and C(9) rings and
C(17), C(18), and C(19) rings (Figure 2), and the torsion angles
associated with the bay C atoms C(4)-C(5)-C(6)-C(7) and C(14)-
C(15)-C(16)-C(17) are nearly the same, with a value of 39.45
and 40.438, respectively,[8] which is close to the reported value
of Cl8-PTCDI (37 and 388).[5] The desired tetrabromotetrachloro-
perylene diimides 6 (Br4Cl4-PDI) were obtained by the imidiza-
tion with n-octylamine or 2,6-diisopropylaniline in glacial acetic
acid in moderate yields, subsequently they were used as pre-
cursors for straightforward transformation with electron-with-
drawing fluoride, cyanide, as well as electron-donating amine
and thiophenol (Scheme 1).
Figure 2. Single crystal of compound 5, showing a twisted perylene back-
bone.
&
&
Chem. Eur. J. 2014, 20, 1 – 6
www.chemeurj.org
2
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Communication
the maximum absorption of Cl4F4-PDI 7 is hypso-
chromically shifted to 496 nm. Introduction of four
arylthio substituents at the perylene core causes an
obvious bathochromic shift with a maximum at
558 nm for compound 9. The more strongly electron-
donating arylamino substituents at the perylene core
evoke a further redshift of the absorption band, for
example, the absorption band of 10a shows an ab-
sorption maximum wavelength at 632 nm. As we ex-
pected, the absorption of the BCCD 11 is much red-
shifted to the near-infrared region with a maximum
wavelength at about 716 nm for 11 a and 720 nm for
11 b, in contrast with their precursors 10a and 10b,
which could be attributed to the extension of the
conjugated system along the laterally annulated car-
bazole rings as well as the intramolecular donor–ac-
Scheme 2. [Pd2(dba)3], P(tBu)3, K3PO4, 1,4-dioxane, reflux, argon, 11 a (45%), 11 b (32%).
dba=dibenzylideneacetone.
(9) and amino (10) groups would bring chromophores with ex-
cellent absorption properties, which could be used for efficient
light-harvesting in supramolecular antennae systems.[12] This
highly regioselective non-bay functionalization protocol is effi-
cient, probably due to the combination of steric effect and re-
activity difference between bromo and chloro substituents.
Further extension of the conjugated systems is expected to
be carried out by intramolecular ring fusion because of the re-
taining chlorines at the bay regions. Direct CÀH functionaliza-
tion has proved to be a special and efficient tool for carbon–
carbon bond formation in organic synthesis.[13] In particular, in-
tramolecular direct arylation reactions employ tethers to limit
the degree of freedom in a system, thereby controlling the re-
gioselectivity of the reaction. Thus, an expedient synthesis of
biscarbazolo[2,3-b]carbazole diimides (BCCD) 11 a and 11 b can
be achieved with tris(dibenzylideneacetone)dipalladium(0) as
a catalyst, tri-tert-butylphosphine as a ligand, and K3PO4 as
Figure 3. UV/vis absorption spectra of tetrachlorotetrasubstituted PDIs: 6a
(red), 7 (olive), 8 (black), 9 (cyan), 10a (purple), and biscarbazolo[2,3-b]carba-
zole diimides 11 a (blue) in chloroform (top), and comparison with TDDFT/
PBE1PBE/6-31G*/PCM computed spectra not including vibronic structures
(bottom).
a base in 1,4-dioxane from tetrachlorotetraamino-PDIs 10a and
10b in moderate yields (Scheme 2).[14] This fourfold intramolec-
ular cyclization to afford these unique propeller-shaped mole-
cules with p-extended system is really efficient if calculated
with average yield per CÀC coupling.[15] The extension of con-
jugated p-systems would lead to molecules with desirable
electronic properties and reduced HOMO–LUMO gaps for ap-
plications in organic electronics and organic photovoltaic devi-
ces.[16] All these core per-substituted PDIs and BCCD have
good solubility in common organic solvent, such as dichloro-
methane, chloroform, and THF etc. and all these new com-
pounds are characterized by mass spectrometry and 1H and
13C NMR spectroscopy (for details see the Supporting
Information).
ceptor interactions. The broad and NIR absorption of BCCD im-
plies that these kinds of derivatives could be potential objects
in solar cells.[16] The fluorescence spectra of these compounds
are also characterized and summarized in Table 1, Table S1
(Supporting Information), and Figure S3 (Supporting Informa-
tion). Both of the Br4Cl4-PDIs 6a and 6b are weakly fluorescent
with a quantum yield of about 4.0%. The Cl4F4-PDI 7 exhibits
an increased quantum yield of 67.4% with an emission maxi-
mum at 532 nm, whereas Cl4CN4-PDI 8 has a relatively low
quantum yield of 10.4%. Furthermore, BCCDs 11 a and 11 b are
very weakly fluorescent (Ffl =1.0%) with an emission band
maxmium at about 740 nm, while tetrachlorotetrathio PDIs
and tetrachlorotetraarylamino PDIs are not fluorescent.
Room temperature absorption spectra of the compounds 6–
11 are shown in Figure 3 and Figure S2 (Supporting Informa-
tion), in which a comparison with TDDFT/PBE1PBE/6-31G*/PCM
spectra, computed at the optimized geometries (Figure S5), is
also reported. As we expected, the functionalization of PDIs by
non-bay region substitution has triggered an eminent progress
in controlling the optical and redox properties. The presence
of the bromo and cyano substituents on the 2,5,8,11-positions
of PDI does not shift significantly the absorption maximum,
The theoretical absorption spectra from 6 to 11 largely
agree well with the experimental spectra (Figure 3 and Figur-
es S2 and S6–S13 in the Supporting Information). The spectral
redshift can be traced back to a reduction in the HOMO–
Chem. Eur. J. 2014, 20, 1 – 6
www.chemeurj.org
3
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Communication
Br4Cl4-PDI 6a is less negative at À0.63 and À0.81 V. Further-
more, a progressive enhancement of the electron affinity is ob-
served from Cl4F4-PDI 7 to Cl4CN4-PDI 8, showing a half-wave
reduction potential wave at À0.66 and À0.88 V for 7 and
À0.21 and À0.56 V for 8, which indicates that 8 are considera-
bly stronger electron acceptors with progressively increased
electron affinity. For the tetrachlorotetrathio-PDI 9, there are
two reversible reduction potentials (À0.75 and À0.94 V),
whereas for the tetrachlorotetraamino-PDIs 10, significantly
lower reduction potentials were observed (À0.98 and À1.09 V
for 10a, À0.93 and À1.05 V for 10b, À0.95 and À1.07 V for
10c). Furthermore, In contrast to the corresponding 10a and
10b, two more negative reversible reduction potentials (À1.27
and À1.45 V for 11 a, À1.22 and À1.44 V for 11 b) and another
additional two reversible positive oxidative potentials (0.98
and 1.31 V for 11 a, 1.02 and 1.35 V for 11 b) can be observed
within the available potential range, which implies that the
fusion of the electron-rich carbazole rings has greatly changed
their redox properties.[16b]
Table 1. Optical and electronic properties of compounds 6–11.
Comp.
labs [nm][a] lem [nm] E1r [V][c] ELUMO [eV][d]
Eg [eV][e]
PDI[f]
6a
6b
7
8
9
10a
10b
10c
11 a
11 b
520 (528)
525 (534)
528 (534)
496 (503)
525 (545)
558 (598)
632 (632)
636 (632)
612 (623)
716 (695)
720 (695)
546
574
582
532
554
–
–
–
–
742
746
À0.84
À0.63
À0.56
À0.66
À0.21
À0.75
À0.98
À0.93
À0.95
À1.27
À1.22
À4.13 (À4.10)
À4.24 (À4.36)
2.27 (2.26)
2.22 (2.24)
À4. 31 (À4.36) 2.18 (2.24)
À4.21 (À4.28)
À4.65 (À4.89)
À4.11 (À4.10)
À3.88 (À3.74)
À3.93 (À3.74)
À3.91 (À3.79)
À3.64 (À3.43)
À3.67 (À3.43)
2.31 (2.37)
2.19 (2.19)
1.89 (1.96)
1.65 (1.82)
1.64 (1.82)
1.72 (1.82)
1.64 (1.73)
1.63 (1.73)
[b]
[b]
[b]
[b]
[a] Peak in the visible region. [b] No fluorescence. [c] Half-wave reduction
potential (V vs. Fc/Fc+) measured in CH2Cl2 with a scan rate of 0.1 VsÀ1
.
[d] Estimated from the onset potential of the first reduction wave, apply-
ing the equation ELUMO =À(4.80+E1r). [e] Obtained from the edge of the
absorption spectra, Eg =1240/lonset. [f] N,N’-bis(octyl)perylene-1,6,7,12-tet-
rachloro-3,4:9,10-tetracarboxylic acid diimides. Theoretical PBE1PBE/6-
31G*/PCM predictions in parentheses (see the Supporting Information for
details).
The LUMO levels of these PDIs and BCCD derivatives could
be obtained from the reduction potentials discussed above, ac-
cording to the calculations (Table 1), all of the LUMO levels of
6a, 6b, 7, and 8 with four electron-withdrawing groups at
non-bay regions are below À4.20 eV, particularly, the LUMO
value of the Cl4CN4-PDI (À4.65 eV) is the lowest reported value
for PDI derivatives, which indicates that they could serve as air
stable n-type organic semiconductors. Region-selective donor-
group-functionalized PDIs had the effect of not significantly
changing the LUMO levels compared with those of Cl4-PDI
(À4.11 for 9, À3.88 for 10a, À3.93 for 10b, and À3.91 eV for
10c), which are consistent with the calculated electron distri-
bution of the LUMO of 10a, mainly focused on the PDI skele-
tons (Figure 4). Moreover, the BCCD derivatives have signifi-
cantly higher LUMO levels with energies of À3.64 and
À3.67 eV for 11 a and 11 b, respectively. The HOMO levels cal-
culated from the onset of the first oxidation wave are
À5.21 eV for 11 a and À5.25 eV for 11 b, the relatively higher
LUMO levels of these new p extension system could also be
explained from the theoretical calculation (Figure 4), both of
the LUMO and HOMO levels are delocalized over the whole p
system. The HOMO–LUMO band gaps of 11 a and 11 b calculat-
ed from CV experiments agree well with the band gaps ob-
tained from the edge of UV/Vis absorption spectra.
Figure 4. Energies and shapes of PBE1PBE/6-31G*/PCM frontier orbitals
(HOMO and LUMO) of model Br4Cl4-PDI 6, tetrachlorotetraamino-PDI 10a,
and biscarbazolo[2,3-b]carbazole diimides 11 a.
LUMO gap from 6 to 11 (Figure 4), due to a more pronounced
rise of the HOMO compared to the LUMO. For the HOMO of
10a, the aromatic system favors to extend from the core
across to outer phenyl rings in the upper half of the molecule
mediated by a 3p orbital of Cl. Together with the quasi-degen-
erate HOMO-1, which is delocalized over the lower half of the
molecule 10a, this gives rise to the double peak around
600 nm.
In conclusion, a new building block of Br4Cl4-PTCDA for
core-persubstituted perylene diimides has been synthesized ef-
ficiently. We have prepared a new series of 1,6,7,12-tetrachloro-
2,5,8,11-tetrasubstituted perylene diimides (Cl4X4-PDIs) by re-
gioselective functionalization of bromine atoms at the non-bay
regions. Notably, we can also extend the system along the lat-
eral axis by fusion of additional few carbazole rings by retain-
ing chlorine atoms to achieve biscarbazolo[2,3-b]carbazole dii-
mides by intramolecular direct arylation of palladium-catalyzed
CÀH functionalization. In light of their unique structure and at-
tractive photophysical and optoelectronic properties, this new
molecular skeleton would be a novel promising candidate for
various applications.
To gain further insight into the electronic properties of core-
tetrachlorotetrasubstituted PDIs, cyclic voltammetries (CVs)
were performed in dichloromethane (Table 1 and Figure S4,
Supporting Information). Compounds 6–11 exhibit two reversi-
ble reduction waves, whereas 11 a and 11 b exhibit additionally
two reversible oxidation waves. In contrast to reference Cl4-
PDI, which shows a half-wave potential E1/2 at À0.84 and
À1.03 V (vs. Fc/Fc+), the half-wave reduction potential of
&
&
Chem. Eur. J. 2014, 20, 1 – 6
www.chemeurj.org
4
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Communication
Yoo, J. Yang, T. Sasamori, N. Tokitoh, T. Cꢃdric, H. Kageyama, D. Kim, H.
Shinokubo, A. Osuka, Chem. Eur. J. 2009, 15, 7530–7533.
Acknowledgements
[5] M. Gsꢂnger, J. H. Oh, M. Kçnemann, H. W. Hçffken, A. Krause, Z. Bao, F.
Wꢁrthner, Angew. Chem. 2010, 122, 752–755; Angew. Chem. Int. Ed.
2010, 49, 740–743.
For financial support of this research, we thank the National
Natural Science Foundation of China (21225209, 21190032, and
91027043), 973 Program (Grant 2011CB932301 and
2013CB933503), NSFC-DFG Joint Project TRR61, and Chinese
Academy of Sciences.
[6] a) W. Yue, A. Lv, J. Gao, W. Jiang, L. Hao, C. Li, Y. Li, L. E. Polander, S.
Barlow, W. Hu, S. Di Motta, F. Negri, S. R. Marder, Z. Wang, J. Am. Chem.
Soc. 2012, 134, 5770–5773; b) W. Yue, J. Gao, Y. Li, W. Jiang, S. Di Motta,
F. Negri, Z. Wang, J. Am. Chem. Soc. 2011, 133, 18054–18057; c) H. Qian,
W. Yue, Y. Zhen, S. Di Motta, E. Di Donato, F. Negri, J. Qu, W. Xu, D. Zhu,
Z. Wang, J. Org. Chem. 2009, 74, 6275–6282; d) Y. Shi, H. Qian, Y. Li, W.
Yue, Z. Wang, Org. Lett. 2008, 10, 2337–2340; f) H. Qian, F. Negri, C.
Wang, Z. Wang, J. Am. Chem. Soc. 2008, 130, 17970–17976; g) H. Qian,
Z. Wang, W. Yue, D. Zhu, J. Am. Chem. Soc. 2007, 129, 10664–10665.
[7] J. Gao, C, Xiao, W. Jiang, Z. Wang, Org. Lett. 2014, 16, 394–397.
[8] CCDC-899277 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[9] F. Wꢁrthner, P. Osswald, R. Schmidt, T. E. Kaiser, H. Mansikkamꢂki, M. Kç-
nemann, Org. Lett. 2006, 8, 3765–3768.
[10] a) W. Yue, T. He, M, Stolte, F, Wꢁrthner, Chem. Commun. 2014, 50,
545–547; b) S.-L. Suraru, U. Zschieschang, H. Klauk, F. Wꢁrthner, Chem.
Commun. 2011, 47, 1767–1769; c) M. C. R. Delgado, E.-G. Kim, D. A. S.
Filho, J.-L. Bredas, J. Am. Chem. Soc. 2010, 132, 3375–3387; d) R. T.
Weitz, K. Amsharov, U. Zschieschang, E. Barrena Villas, D. K. Goswami, M.
Burghard, H. Dosch, M. Jansen, K. Kern, H. Klauk, J. Am. Chem. Soc.
2008, 130, 4637–4645.
[11] C. Rçger, F. Wꢁrthner, J. Org. Chem. 2007, 72, 8070–8075.
[12] a) S. L. Suraru, F. Wꢁrthner, J. Org. Chem. 2013, 78, 5227–5238; b) D.
Bialas, S. L. Suraru, R. Schmidt, F. Wꢁrthner, Org. Biomol. Chem. 2011, 9,
6127–6132; c) C. Rçger, M. G. Mꢁller, M. Lysetska, Y. Miloslavina, A. R.
Holzwarth, F. Wꢁrthner, J. Am. Chem. Soc. 2006, 128, 6542–6543.
[13] a) S. L. Suraru, C. Burschka, F. Wꢁrthner, J. Org. Chem. 2014, 79, 128–
139; b) W. Liu, H. Cao, J. Xin, L. Jin, A. Lei, Chem. Eur. J. 2011, 17, 3588–
3592; c) C. Sun, H. Li, D. Yu, M. Yu, X. Zhou, X. Lu, K. Huang, S. Zheng, B.
Li, Z. Shi, Nat. Chem. 2010, 2, 1044–1049; d) D. Alberico, M. E. Scott, M.
Lautens, Chem. Rev. 2007, 107, 174–238; e) Z. Liu, R. Larock, Tetrahedron
2007, 63, 347–355; f) L. Campeau, M. Parisien, A. Jean, K. Fagnou, J.
Am. Chem. Soc. 2006, 128, 581–590.
Keywords: perylene diimides · intramolecular arylation · non-
bay regions · palladium · regioselectivity
[1] For selected recent reviews: a) H. Usta, A. Facchetti, T. J. Marks, Acc.
Chem. Res. 2011, 44, 501–510; b) X. Zhan, A. Facchetti, S. Barlow, T. J.
Marks, M. A. Ratner, M. R. Wasielewski, S. R. Marder, Adv. Mater. 2011, 23,
268–284; c) F. Wꢁrthner, M. Stolte, Chem. Commun. 2011, 47, 5109–
5115.
[2] a) Q. Yan, Y. Zhou, Y. Q. Zheng, J. Pei, D. Zhao, Chem. Sci. 2013, 4, 4389–
4394; b) C. Li, M. Y. Liu, N. G. Pschirer, M. Baumgarten, K. Mꢁllen, Chem.
Rev. 2010, 110, 6817–6855; c) R. F. Kelley, W. S. Shin, B. Rybtchinski, L. E.
Sinks, M. R. Wasielewski, J. Am. Chem. Soc. 2007, 129, 3173–3181; d) R.
Schmidt, M. M. Ling, J. H. Oh, M. Winkler, M. Kçnemann, Z. Bao, F.
Wꢁrthner, Adv. Mater. 2007, 19, 3692–3695; e) C. Ego, D. Marsitzky, S.
Becker, J. Zhang, A. C. Grimsdale, K. Mꢁllen, J. D. MacKenzie, C. Silva,
R. H. Friend, J. Am. Chem. Soc. 2003, 125, 437–443; f) L. Schmidt-
Mende, A. Fechtenkçtter, K. Mꢁllen, E. Moons, R. H. Friend, J. D. Mac-
Kenzie, Science 2001, 293, 1119–1122.
[3] a) C. Huang, S. Barlow, S. R. Marder, J. Org. Chem. 2011, 76, 2386–2407;
b) W. Jiang, Y. Li, W. Yue, Y. Zhen, J. Qu, Z. Wang, Org. Lett. 2010, 12,
228–231; c) Y. Li, L. Tan, Z. Wang, H. Qian, Y. Shi, W. Hu, Org. Lett. 2008,
10, 529–532; d) P. Rajasingh, R. Cohen, E. Shirman, L. J. W. Shimon, B.
Rybtchinski, J. Org. Chem. 2007, 72, 5973–5979; e) H. Qian, C. Liu, Z.
Wang, D. Zhu, Chem. Commun. 2006, 4587–4589; f) L. Fan, Y. Xu, H.
Tian, Tetrahedron Lett. 2005, 46, 4443–4447; g) P. Osswald, D. Leusser,
D. Stalke, F. Wꢁrthner, Angew. Chem. 2005, 117, 254–257; Angew. Chem.
Int. Ed. 2005, 44, 250–253; h) B. A. Jones, M. J. Ahrens, M. H. Yoon, A.
Facchetti, T. J. Marks, M. R. Wasielewski, Angew. Chem. 2004, 116, 6523–
6526; Angew. Chem. Int. Ed. 2004, 43, 6363–6366; i) M. J. Ahrens, M. J.
Fuller, M. R. Wasielewski, Chem. Mater. 2003, 15, 2684–2686; j) H.
Langhals, S. Kirner, Eur. J. Org. Chem. 2000, 365–380; k) Y. Zhao, M. R.
Wasielewski, Tetrahedron Lett. 1999, 40, 7047–7050; l) U. Rohr, P.
Schlichting, A. Bçhm, M. Gross, K. Meerholz, C. Brꢂuchle, K. Mꢁllen,
Angew. Chem. 1998, 110, 1463–1467; Angew. Chem. Int. Ed. 1998, 37,
1434–1437.
[14] S. Hostyn, B. U. W. Maes, L. Pieters, G. L. F. Lemiꢄre, P. Mꢅtyus, G. Hajꢆs,
R. A. Dommisse, Tetrahedron 2005, 61, 1571–1577.
[15] E. A. Jackson, B. D. Steinberg, M. Bancu, A. Wakamiya, L. T. Scott, J. Am.
Chem. Soc. 2007, 129, 484–485.
[16] a) Y. Lin, Y. Li, X. Lin, Chem. Soc. Rev. 2008, 37, 827–838; b) S.-L. Suraru,
U. Zschieschang, H. Klauk, F. Wꢁrthner, Chem. Commun. 2011, 47,
11504–11506.
[4] a) G. Battagliarin, C. Li, V. Enkelmann, K. Mꢁllen, Org. Lett. 2011, 13,
3399–3401; b) T. Teraoka, S. Hiroto, H. Shinokubo, Org. Lett. 2011, 13,
2532–2535; c) S. Nakazono, S. Easwaramoorthi, D. Kim, H. Shinokubo,
A. Osuka, Org. Lett. 2009, 11, 5426–5429; d) S. Nakazono, Y. Imazaki, H.
Received: January 30, 2014
Published online on && &&, 0000
Chem. Eur. J. 2014, 20, 1 – 6
www.chemeurj.org
5
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ

Communication
COMMUNICATION
Organic electronics: A series of novel
chromophores were afforded by regio-
selective functionalization of core per-
substituted perylene diimides (PDIs)
(see scheme). Furthermore, new BCCD
derivatives with an extended p-conju-
gated system were synthesized by
direct palladium-catalyzed intramolecu-
lar ring fusion.
&
Materials Chemistry
W. Yue, W. Jiang,* M. Bçckmann,
N. L. Doltsinis, Z. Wang*
&& – &&
Regioselective Functionalization of
Core-Persubstituted Perylene Diimides
&
&
Chem. Eur. J. 2014, 20, 1 – 6
www.chemeurj.org
6
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!