One-Pot Domino Carbonylation Protocol for Aromatic Diimides toward n-Type Organic Semiconductors

Article abstract of DOI:10.1002/anie.202003179

Aromatic diimides are one of the most important chromophores in the construction of n-type organic semiconductors, which lag far behind their p-type counterpart but are necessary for ambipolar transistors, p-n junctions and organic complementary circuits. Herein, we establish a facile one-pot domino synthetic protocol for aromatic diimides via palladium-catalyzed carbonylation of tetrabromo aromatic precursors. Taking tetrabromocorannulene (TBrCor) and tetrabromo-2,7-di-tert-butylpyrene (TBrPy) as the typical examples, we obtained diimide derivatives in yields of about 50 percent, one order of magnitude higher than that of the traditional multi-step diimidization. As demonstrated in the case of corannulene diimide, the efficient diimidization not only allows the LUMO levels to be lowered significantly but also provides an ordered and closer packing structures, opening up possibilities to the development of n-type semiconducting materials based on a variety of aromatic systems.

Full text of DOI:10.1002/anie.202003179

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: One-Pot Domino Carbonylation Protocol for Aromatic Diimides
toward n-type Organic Semiconductors
Authors: Xiaolong Fu, Yonggang Zhen, Zhenjie Ni, Yang Li, Huanli
Dong, Jay S. Siegel, and Wenping Hu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202003179
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10.1002/anie.202003179
Angewandte Chemie International Edition
COMMUNICATION
One-Pot Domino Carbonylation Protocol for Aromatic Diimides
toward n-type Organic Semiconductors
Xiaolong Fu, Yonggang Zhen*, Zhenjie Ni, Yang Li, Huanli Dong, Jay S. Siegel and Wenping Hu
Abstract: Aromatic diimides are one of the most important
chromophores in the construction of n-type organic semiconductors,
which lag far behind p-type counterpart but is necessary for the
ambipolar transistors, p–n junctions and organic complementary
circuits. Herein, we establish a facile one-pot domino synthetic
protocol for aromatic diimides via palladium-catalyzed carbonylation
of tetrabromo aromatic precursors. Taking tetrabromocorannulene
(TBrCor) and tetrabromo-2,7-di-tert-butylpyrene (TBrPy) as the
typical examples, we achieved diimide derivatives in yields about
50%, one order of magnitude higher than that of the traditional multi-
step diimidization. As demonstrated in the case of corannulene
diimide, the efficient diimidization not only allows the LUMO levels to
be lowered significantly but also provides an ordered and closer
packing structures, opening up possibilities to the development of n-
type semiconducting materials based on a variety of aromatic
systems.
(ADI),[7] pyrene diimides (PyDI),[8] perylene diimides (PDI)[6a, 6d, 9]
as well as biazulene diimides (BAzDI)[10]. Previously we reported
single crystals of tetrachlorinated diperylene diimide with an
electron mobility as high as 4.65 cm2 V-1 s-1.[9b] The electron
mobilities from NDI- and PDI-based small molecules have
reached up to 8.6 and 6.0 cm2 V-1 s-1, respectively.[6d, 11] PyDI
derivatives exhibit efficient electron transport properties with
electron mobility up to 3.08 cm2 V-1 s-1.[8c] However, a long-
standing issue hindering the development of novel aromatic
diimides is the inefficient and tedious multistep syntheses
requiring cyanation, hydrolysis, dehydration and imidization
(Figure 1).
The last two decades has witnessed tremendous progress in
organic semiconductors with widespread applications in organic
field effect transistors (OFETs)[1], organic solar cells (OPVs)[2],
and organic light-emitting diodes (OLED)[3]. However, n-type
organic semiconductors lag far behind p-type counterpart in
terms of molecular diversity, carrier mobility as well as air
stability, preventing the development in the ambipolar transistors,
p–n junctions and organic complementary circuits.[4]
Diimidization of aromatic systems can enhance electron affinity
values significantly, thus opening up the possibility to achieve
promising n-type materials including pyromellitic diimides
(PMDI),[5] naphthalene diimides (NDI),[6] anthracene diimides
[a]
Dr. F. X. Fu, Prof. Y. G. Zhen, Dr. J. Zhen, Dr. Y. Li, Prof. H. L.
Dong, Prof. W. P. Hu
Institute of Chemistry, Chinese Academy of Sciences (ICCAS)
Beijing 100190, China
E-mail: zhenyg@iccas.ac.cn
Prof. J. S. Siegel
School of Pharmaceutical Science and Technology, Tianjin
University, 92 Weijin Road, Nankai District, Tianjin 300072, China
Prof. W. P. Hu
Key laboratory of Molecular Optoelectronic Sciences, School of
Science, Tianjin University, Tianjin 300072, China
Joint School of National University of Singapore and Tianjin
University, International Campus of Tianjin University, Binhai New
City, Fuzhou 350207, China
Figure 1. Representative aromatic diimides and the usual multi-step synthetic
route from tetrabromo-precusors.
[b]
The authors acknowledge the Shanghai Synchrotron Radiation
Facility (BL17U1) for the XRD measurements. They really
appreciate Prof. Fengyu from BL17U1 and Miss Tongling Liang from
ICCAS for resolving the single-cystal structures, Prof. Junfeng Xiang
from ICCAS for NMR analysis and Mrs. Panpan Yu from Tianjin
Univerisity for UV-vis absorption spectra measurement. They are
grateful for the financial support from the National Natural Science
Foundation of China (51822308, 51733004, 21975263, 51725304,
51633006, 21661132006), the Ministry of Science and Technology
Although aromatic imides can be judiciously prepared through
Friedel–Crafts reaction between aromatic carbonyl chlorides and
isocyanates in the presence of aluminum chloride,[12] Heck-style
palladium-catalyzed carbonylation to form amides[13] rarely has
been used to achieve diimide derivatives mainly because of the
low-yield domino carbonylation reactions.[14] Herein, we report a
facile one-pot palladium-catalyzed carbonylation diimidization of
tetrabrominated aromatic rings, and optimize the reaction
parameters of CO source, catalyst ligand field, Brønsted base
and solvent. Taking tetrabromocorannulene (TBrCor) and
tetrabromo-2,7-di-tert-butylpyrene (TBrPy) as lead examples, we
of
China
(Grants
2016YFB0401100,
2015CB856502,
2017YFA0204503), the Youth Innovation Promotion Association of
the Chinese Academy of Sciences.
[c]
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.202003179
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COMMUNICATION
achieved diimide derivatives in yields about 50%, one order of
Applying these optimized conditions on TBrPy and butylamine
yields pyrene diimide (PyDI) in 54% yield (Scheme 1). Despite a
slightly lower yield, use of Mo(CO)6 is more convenient and less
dangerous than CO gas. Mo(CO)6 became the best practice CO
source when demonstrating the substrate scope of the domino
carbonylation protocol (Table S1). For aliphatic amines we
observed higher yields with short-chain amines, which is similar
to the case of phthalimides.[19] The carbonylation reaction of 1,8-
dibromobenzene proceeded smoothly even with unsubstituted
aniline possessing relatively low nucleophilicity, which was not
observed for 1,2-dibromobenzene.[19] Very interestingly, we
found that the replacement of unsubstituted aniline by bulky 2,6-
di(isopropyl) substituted aniline led to the formation of
isonaphthalimide due to the big steric hindrance. Thus we
proposed two pathways for the carbonylation protocol in term of
the steric effect (Scheme 2). Unsubstituted or dimethyl
substituted tetrabromobenzene gave moderate yields while
tetrachlorobenzene afforded no detectable product. The one-pot
Pd-catalyzed carbonylative diimidization is relatively efficient
15]
magnitude higher than traditional methods.[8c,
The electron
affinity values increase by more than 1 eV relative to the parent
compounds. Notably, corannulene diimide (CorDI) assembles
into one dimensional microribbons with close face-to-face π-π
stacking, thus facilitating electron carrier transport with carrier
mobility up to 0.05 cm-2 V-1 s-1 – one of the highest mobilities for
corannulene derivatives.[16]
Table 1. Optimization of reaction conditions.
Entry
Catalyst/Ligand
(3 mol %)
CO
source
Solvent
Base
Yielda
(%)
1
2
Pd(OAc)2
Pd(OAc)2
CO
CO
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Xylene
DBU
DABCO
KOH
CsOH
DBU
11
trace
n.d.b
n.d.b
7
(30–70
% yield) in contrast to the traditional multi-step
3
Pd(OAc)2
CO
diimidization (2–5% yield).[8c, 15]
4
Pd(OAc)2
CHCl3
Mo(CO)6
CO
Scheme 2. Two possible pathways for the carbonylation protocol.
5
Pd(OAc)2
6
Pd(OAc)2/tBu3PHBF4
Pd(OAc)2/Xantphos
Pd(OAc)2/Ad2PnBu
Pd(OAc)2/Ad2PnBu
Pd(OAc)2/Ad2PnBu
Pd(OAc)2/Ad2PnBu
DBU
23
7
CO
DBU
14
8
CO
DBU
52
9
CO
DBU
trace
9
10
11
CO
DMAc
DBU
Mo(CO)6
Toluene
DBU
41
a. Isolated yields. b. Not dected.
For our initial investigation of the intramolecular
decarboxylative coupling, we chose the readily available
TBrCor,[17] CO (1 atm), and butylamine as a test substrate
(Table 1). Inspired by Alper's catalyst,[18] we first attempted a
combination of Pd(OAc)2 (3 mol %) as the catalyst and DBU as
The electrochemical properties of CorDI and PyDI were
investigated using cyclic voltammetry using Ag/AgCl as
reference electrode, platinum as working electrode and
ferrocene as internal standard. The cyclic voltammograms for
CorDI and PyDI showed two reversible reduction waves in a
negative potential range from –1.0 to –2.5 eV versus ferrocene
(Fc/Fc+; Figure 2a). From the first half-wave reduction potentials,
we estimated LUMO levels of –3.50 eV for CorDI and –3.26 eV
for PyDI, which are 1.16 and 1.57 eV lower compared with
o
the base in toluene at 110 C for 24 h. and found the yield of
CorDI was only 11%. Studies on the Brønsted base revealed
that DABCO and KOH were ineffective at promoting the desired
transformation. Changing the CO source to chloroform with
CsOH gave no detectable product; however, Mo(CO)6 was a
possible safer alternative albeit with slightly less efficiency.
t
Screening the ligand series Bu3PHBF4, Xantphos and Ad2PnBu
(CataCXium A) produced CorDI in 23%, 14%, and 52% yields,
respectively. Replacing toluene with another low-polarity solvent
xylene or the polar solvent DMAc gave much lower yield. These
optimization studies showed that the bulky and election-rich
ligand Ad2PnBu enhanced the yield significantly, such that
replacing CO with the safer reagent Mo(CO)6 still afforded a 41%
unmodified
corannulene[15]
and
2,7-di-tert-butylpyrene[8c]
respectively, demonstrating the strong electron-withdrawing
ability of diimides group. CorDI's first reduction potential is
remarkably similar to that found for azaindenocorannulene
monoimde.[20]
CorDI or PyDI shows a maximum absorption peak at 392 or
426 nm in contrast to that of corannulene or pyrene with a
maximum peak at 288 or 337 nm respectively (Figure 2b).[8c]
After diimidization of corannulene and pyrene, the absorption
spectra show a large bathochromic shift of 80~100 nm as a
result of π-conjugated structure extension. The band gaps (Eg)
calculated from the absorption spectra were 2.87 eV for CorDI
and 2.67 eV for PyDI respectively.
yield
of
CorDI
in
the
optimized
conditions
(Pd(OAc)2/Ad2PnBu/DBU/Toluene).
Scheme 1. Optimized conditions for the synthesis of PyDI.
Density functional theory (DFT) calculations for highest
occupied molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) levels of CorDI and PyDI relative to
corannulene and pyrene were performed at Gaussian B3LYP/6-
31+g(d,p) level (Figure 2c). The LUMO/HOMO levels of
corannulene, CorDI, pyrene and PyDI were calculated to be –
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1.58/–5.96, –3.10/–6.59, –1.49/–5.35 and –3.12/–5.98 eV
respectively, also suggesting the introduction of diimide group
significantly lowers the LUMO levels. CorDI maintains the bowl-
shaped structure similar to corannulene while PyDI molecule
adopts a planar and rigid conjugated backbone like pyrene. The
LUMO electron density of CorDI and PyDI delocalizes all over
the entire molecular structure while the HOMO electron density
localizes mainly on the parent aromatic cores.
compensate the dipole moment induced from the bowl-in-bowl
stacking. PyDI single crystal belongs to the monoclinic P21/c
space group crystal with lattice constants a = 6.16 Å, b = 10.28
Å, c = 24.14 Å, α = γ = 90°, β = 96.35°. As shown in Figure 3b,
five-membered imide rings were coplanar with the pyrene core,
thus extending the π-conjugated system. Due to the steric
hindrance effects of tert-butyl group, PyDI molecules also adopt
one-dimensional slipped stacking arrangement with an
intermolecular π-π distance of 3.39 Å but a small π-orbital
overlap along a axis (Figure 3d,f). In ab plane, all the stacks
orientate in the same direction while in ac plane the
neighbouring stacks have a dihedral angle of 68.13° in term of
the pyrene plane with very weak tert-butyl C-H···O
intermolecular interactions (Figure 3f).
a
b
PyDI
CorDI
corannulene
CorDI
pyrene
PyDI
a
b
-2.5 -2.0 -1.5 -1.0 -0.5
250 300 350 400 450 500
Wavelength (nm)
E (V) vs. Fc/Fc+
1.39 Å
c
PyDI
pyrene
corannulene
CorDI
0.82 Å
LUMO
top view side view
top view
side view
d
c
HOMO
c
o
(b)
c
a
Figure 2. (a) Cyclic voltammetry of CorDI and PyDI in CH2Cl2 solution using
Ag/AgCl as reference electrode and ferrocene as internal standard. (b)
Normalized UV-Vis absorption spectra of Corannulene (magenta line), CorDI
(red line), pyrene (navy line) and PyDI (blue line) in CH2Cl2 solution. (c)
Frontier molecular orbital diagrams of Corannulene, CorDI, pyrene and PyDI.
o
a
b
f
e
To elucidate the relationship between molecular structures
and packing structures, crystals of CorDI and PyDI suitable for
single-crystal X-ray structure analysis were obtained by slow
evaporation of CHCl3/CH3OH and toluene solutions respectively
at room temperature. It should be noted that the crystal of CorDI
could only be resolved by the synchrotron radiation facility due
to the very small size.[21] Although the resolution and
completeness of single-crystal diffraction data is not high, the
information about cell parameters and packing arrangement is
reliable. CorDI single crystal belongs to the triclinic P-1 space
group with lattice constants a = 7.19 Å, b = 16.35 Å, c = 20.88 Å,
α = 82.01°, β = 83.78°, γ = 88.86°. In the structure of CorDI the
bowl-shaped configuration of corannulene core is retained with a
slight rim-to-hub bowl depth decrease from ~0.87 Å to ~0.82 Å
after diimidization. The ear depth from hub carbon atoms to the
plane defined by the four ear-like carbonyl carbon atoms is
~1.39 Å (Figure 3a). Whereas the parent corannulene shows a
highly disordered packing structure dominated by C–H···π
interactions, CorDI molecules adopt one-dimensional slipped
stacking motif with very close bowl-in-bowl π-π contacts of 3.29–
3.39 Å and a large π-orbital overlap along a axis (Figure 3c,e).
Beside the intrastack interactions, there are very strong convex-
convex π-π interactions of 3.34–3.36 Å as well as C–H···O
interactions of 2.45–2.69 Å between two adjacent columns
(Figure 3e), which are stacked in an opposite direction to
Figure 3. Single-crystal structures of CorDI (a,c,e) and PyDI (b,d,f). (a,b) Top
views and side views of single molecular structures. (c,d) Packing structures
wherein hydrogen atoms are omitted for clarity. (e,f) Intermolecular π-π or C-
H···O contacts between adjacent molecules.
In view of the large π-orbital overlap and closer packing
structure of CorDI relative to PyDI, we focused on the
investigation of charge transport behaviour of CorDI. Because
single crystals have no grain boundaries as well as less charge
carrier traps and defects, microcrystals of CorDI (Figure 4a)
were grown by drop casting the toluene solution to reveal the
intrinsic electrical characteristics. As shown in the transmission
electron microscope (TEM) image (Figure 4b), highly regular
microribbon-shaped crystals were observed. The corresponding
selected area electron diffraction (SAED) patterns of this
microribbon (Figure 4c) at different areas covering the whole
length were identical, indicating that the whole microribbon was
a single crystal. It can be concluded that the CorDI microribbon
grows along the [100] direction, which coincides with the
columnar π-π stacking of bowl-shaped CorDI molecules.
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carbonylation of tetrabrominated aromatic compounds, in yields
one order of magnitude higher than previous multi-step
syntheses. As demonstrated in the case of corannulene diimide,
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lowered significantly but also provides an ordered and closer
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Keywords: organic semiconductor • domino synthesis •
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COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Aromatic diimides:
domino synthetic protocol for aromatic
diimides via palladium-catalyzed
A
facile one-pot
Xiaolong Fu, Yonggang Zhen*,
Zhenjie Ni, Yang Li, Huanli Dong,
Jay S. Siegel and Wenping Hu
carbonylation has been established. This
methodology not only allows the LUMO
levels to be lowered significantly but also
provides an ordered and closer packing
structures, opening up possibilities to the
development of n-type semiconducting
materials based on a variety of aromatic
systems.
Page No. – Page No.
One-Pot Domino Carbonylation
Protocol for Aromatic Diimides
toward
n-type
Organic
Semiconductors
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