Synthesis and Properties of New N-Heteroheptacenes for Solution-Based Organic Field Effect Transistors

Article abstract of DOI:10.1002/chem.201701966

A series of N-heteroheptacenes was synthesized from ortho-thiophene-substituted aryl azides using a Rh₂^II-catalyzed C?H bond amination reaction to construct the thienoindole moieties. This reaction tolerated the presence of electron-

Full text of DOI:10.1002/chem.201701966

A Journal of
Accepted Article
Title: Synthesis and Properties of New N-Heteroheptacenes for
Solution-Based Organic Field Effect Transistors
Authors: Fei Zhou, Sheng Liu, Bernard D. Santarsiero, Donald J. Wink,
Damien Boudinet, Antonio Facchetti, and Tom G Driver
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
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the VoR from the journal website shown below when it is published
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To be cited as: Chem. Eur. J. 10.1002/chem.201701966
Link to VoR: http://dx.doi.org/10.1002/chem.201701966
Supported by

Chemistry - A European Journal
10.1002/chem.201701966
FULL PAPER
Synthesis and Properties of New N-Heteroheptacenes for
Solution-Based Organic Field Effect Transistors
[
a]
[a]
[b]
[a]
[c]
Fei Zhou, Sheng Liu, Bernard D. Santarsiero, Donald J. Wink, Damien Boudinet, Antonio
[
c]
[a], [d]
Facchetti, and Tom Driver*
[
1g,7]
[8]
Abstract: A series of N-heteroheptacenes was synthesized from
heteroaromatic small molecules,
perylenediimides
(DPP)-based polymers have also emerged
recently as alternatives because of their solubility in organic
solvents facilitates solution-based processing. Devices
constructed with these soluble molecules exhibit hole- and
and
II
[9]
ortho-thiophene-substituted aryl azides using a Rh
2
-catalyzed C–H
diketopyrrole
bond amination reaction to construct the thienoindole moieties. This
reaction tolerated the presence of electron-donating or withdrawing
groups on the aryl azide without adversely affecting the yield of the
amination reaction. The central thiophene ring was created from two
thienoindole pieces through a Pd-catalyzed Stille reaction to install the
thioether followed by a Cu-mediated Ullman reaction to trigger the
cyclization. The photophysical and electrochemical properties of the
resulting focused library of N-heteroheptacenes revealed that the
electronic nature is controlled by the arene substituent while single
crystals grown reveal that the packing motif is influenced by the N-
2
–1 –1
electron mobilities surpassing 5 cm ·V ·s and as high as 15
2
–1 –1 [10]
cm ·V ·s .
Despite these advances, the synthesis of new,
easily tunable organic semiconductors remain of interest in order
to understand the relationship between their molecular structure
and their fundamental properties and to construct solution-
processed devices.
Because of their promise, significant effort has been made to
develop acene- and heteroacene-based solution-processable
field effect transistors. In acenes, solubilizing substituents were
installed to enable the solution-based process and improve the
substituent.
Solution-processed thin-film OFET devices were
fabricated with the N-heteroheptacenes, and one exhibited a hole-
2
–1 –1
mobility of 0.02 cm ·V ·s .
[
11]
stability against oxidation or dimerization (Scheme 1a).
In
addition to improving the solubility, studies on these pentacene
derivatives have shown the substituents also exerted significant
Introduction
[12]
influence on the molecular packing motif in the solid state.
Further, Anthony and co-workers showed that the addition of two
triisopropylsilylalkynyl substituents to the central aromatic ring
The potential optoelectronic applications of semiconducting
polymers and fused-oligomeric aromatic molecules continue to
inspire significant research interest because of their solution
modified
intermolecular electronic interactions.
into the backbone of these acenes improves their stability by
the
intramolecular electronic
structure
and
[4c,13]
Placing heteroatoms
[
1]
processibility and tenability. Ladder-shape linear polyacenes,
such as rubene, pentacene and larger acenes, have been
extensively investigated because of their high carrier mobility in
loweringꢀthe HOMO energy as well as improving their solubility by
[2f,14]
enabling substitution on the heteroatoms.
Accordingly,
[7a,7c,15]
[
1f, 2]
thin-film transistors (Figure 1a).
Impressive performance was
significant attention has been spent on thiophene-
and
heteroacenes to produce promising materials
Scheme 1b). Heteroatom substitution in these materials
produces improved secondary interactions that originate from
[
3]
achieved using pentacene and single crystal rubrene. While
their potential has been limited by difficult processing from
[16]
pyrrole-based
(
[
4]
solution, in recent years significant strides have been made to
improve their environmental stability and solubility in organic
[
5],[6]
solvents.
Thin-film transistors (FETs) based on benzo-fused
(a)
Si(iPr)3
[
[
a]
b]
F. Zhou, Dr. S. Liu, Prof. Dr. D. Wink, Prof. Dr. T. Driver
Department of Chemistry
University of Illinois at Chicago
pentacene
2
µh = 5-40 cm /Vs (single crystal)
Ph Ph
845 West Taylor Street, Chicago, IL, 60607, USA
E-mail: tgd@uic.edu
Prof. Dr. B. D. Santarsiero
Center for Biomolecular Sciences
University of Illinois at Chicago
Si(iPr)3
Ph Ph
rubrene
TIPS-PEN
900 South Ashland Avenue, Chicago, IL, 60607, USA
µh = 0.4 cm /Vs (thin film)
2
2
2
[
c]
b]
Dr. D. Boudinet, Dr. A. Facchetti
Flexterra Inc,
µh = 15 cm /Vs (single crystal)
µh = 2.4 cm /Vs (single crystal)
(b)
8025 Lamon Avenue, Skokie, IL, 60077, USA
H
N
S
[
Prof. Dr. T. G. Driver
Institute of Next Generation Matter Transformation, College of
Chemical Engineering
N
H
S
Huaqiao University
dinaphthothienothiophene (DNTT)
2
668 Jimei Boulevard, Chicago, Fujian, 351021, People’s Republic of
µh = 2.9 cm /Vs (thin film)
indolocabazole (ICZ)
2
2
China
µh = 8.3 cm /Vs (single crystal)
µh = 0.1 cm /Vs (thin film)
Supporting information for this article is given via a link at the end of
the document.
Scheme 1. Ladder-based acenes and heteroacene electronic materials.
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Chemistry - A European Journal
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R1
R1
R1
R1
S
S
S
S
requisite aryl azides 3 for the intramolecular rhodium-catalysed N-
heterocycle formation.
N
R2
S
N
R2
N
R2
N
R2
S
1
8
5
3
2
2
1. (Ph P) PdCl (5 mol %)
S
2
Br
2 3 2
Na CO , H O/dioxane
S
•
Control electronic properties with R1
Control solubility and crystal packing with R2
R1
2
(HO) B
+
1
(1)
R
•
2. tBuONO, Me SiN
MeCN
H
3
3
NH
2
N3
R1
S
S
Br
2
3
S
R1
(HO) B
2
+
R1
NH2
N
H
The thienoindole cores were constructed from aryl azides 3
H
N3
II
[18]
2
3
4
using our Rh
2
-catalysed amination reaction (Table 1). After a
II
brief survey of Rh
2
-carboxylates, the best catalyst for this
II
Scheme 2. Potential synthesis of N-heteroacenes through
ꢀ
Rh
2
-catalyzed C–H
[20]
transformation was found to be Du Bois’s Rh
2
(esp)
2
.
Exposure
bond amination.
of aryl azide 3a to this catalyst produced thienoindole 4a in nearly
quantitative yield. In contrast, thermolysis of 3a produced the
II
thienoindole in only 70% yield. The Rh
2
-catalyzed heterocycle
sulfur to benefit their crystal packing through hydrogen bonding
[
17]
formation could be scaled to 5 mmol without reduction of the yield.
In a similar fashion, electron-rich aryl azide 3f or electron-deficient
aryl azides 3g and 3h were cleanly converted to the analogous
substituted thienoindoles 4f – 4h without any complications. We
anticipated that the presence of the electron-donating or electron-
and sulfur···sulfur- or sulfur···π interactions.
have been used to construct organic field effect devices that
These materials
2
–1 –1
exhibit a FET mobility up to 8.3 cm ·V ·s .
N-heteroheptacenes 1 were targeted because we anticipated
that their electronic- and solubility could be controlled by the
1
1
2
withdrawing R -substituents on these thienoindole scaffolds
choice of the indole R -substituent or nitrogen R -substituent
Scheme 2). We anticipated that these heterocycles could be
would serve as a focused basis set to modulate the electronic
properties of the N-heteroheptacene targets.
(
assembled from two molecules of thienoindole 5 by constructing
the central thiophene ring. N-Alkylation or N-arylation of 4 was
envisioned to control the solubility and potentially the crystal
packing of the target N-heteroacene. A series of thienoindoles 4
would be created from ortho-substituted aryl azides 3 through a
With these thienoindoles in hand, the next stage of the
synthesis was to add a substituent to the nitrogen to attempt to
vary the solubility and crystal-packing properties of the N-
heteroacene targets (Table 2). To improve the solubility of the N-
heteroacene, an n-dodecyl group was added (entry 1). On the
II
[18]
Rh
2
-catalyzed C–H amination reaction.
Our reaction would
enable fine-tuning of the electronic nature of N-heteroheptacene
1
1
by varying the identity of the R -substituents on the arene. The
requisite aryl azides would be constructed from the appropriate 2-
bromoanilines through Suzuki–Miyaura cross-coupling
II
Table 1. Rh
2
-Catalyzed thienoindole synthesis.
2
a
S
S
reaction followed by an azidation reaction. If successful, this
modular route would enable variation of the bulk properties of N-
heteroacene by substituting both the nitrogen- and the indole
portion.
Rh2(esp)2 (5 mol%)
R1
R1
entry
1
H
PhMe, 90 °C
N
H
N3
3
4
a
#
a
aryl azide 3
thienoindole 4
yield, %
S
S
Results and Discussion
b
b
b
b
95(70)
82(66)
91(68)
75(59)
H
N
H
Synthesis of N-heteroacenes
N3
II
A series of ortho-substituted aryl azides 3 for the Rh
2
-catalyzed
S
S
MeO
C–H bond amination reaction were first assembled to create a
focused library of N-heteroheptacenes (eq 1). These substrates
were accessed by cross-coupling commercially available 4- and
MeO
MeO
2
3
4
f
N
H
H
MeO
N3
5
-substituted 2-bromoanilines 2 with thiophene boronic acid.
S
S
Bromoanilines for our study were chosen to contain either
F
F
electron-donating OMe-, electron-neutral H-, or electron-
g
h
N
H
1
H
withdrawing F- or CF
3
R -substituents. At the outset of the study,
N3
we anticipated that electron-withdrawing groups would be
necessary to offset inherent electron-richness of the thienoindole
core. After introduction of the ortho-thiophene substituent using
an unoptimized Suzuki–Miyaura reaction, the azide was installed
S
S
H
F3C
N
H
F3C
N3
[
19]
using conditions reported by Moses and co-workers.
Submission of the anilines to tert-butyl nitrite and trimethylsilyl
[
a] Isolated after silica gel chromatography. [b] Product yield when aryl
azide smoothly converted the 2-substituted anilines to the
azides heated to 150 °C in xylenes for 16 h.
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unsubstituted thienoindole 4a, additional N-alkyl and aryl
substituents were appended to determine their effect on the bulk
properties of the N-heteroacene. A removable SEM group was
attached to determine if the identity of the N-substituent could be
modified at a late stage (entry 2). An n-propyl substituent was
added to see if a short alkyl group would have a positive effect on
the solubility of the acene (entry 3). An isopropyl substituent was
installed to determine if the additional substitution on the
aminomethylene might affect the crystal-packing (entry 4). Finally,
an aryl substituent was added to determine if additional π-π
interactions could be introduced between the stacked acenes
(
entry 5). To an enable comparison to 5a, n-dodecyl groups were
Table 2. N-Alkylation or N-arylation of thienoindole 5.
added to the unsubstituted thienoindoles 4f – 4h (entries 6 – 8).
Together, we anticipated that these N-substituents would enable
us to begin to develop a structure-activity relationship for the N-
heteroacene target.
S
alkyl-Br (1.5 equiv)
S
NaH, DMF
R1
R1
N
H
or
N
Ar-Br (2.5 equiv)
Next, dimerization of the thienoindoles was accomplished by
installing the central thioether bond (Scheme 3). Towards this
R2
4
Pd(OAc)2 (5 mol %)
5
tBu3P (15 mol %), K2CO3, PhMe
end, C2-bromination of
5
was achieved using N-
a
bromosuccinimide. Following the report of Kano and co-
entry
#
thienoindole 4
thienoindole 5
yield, %
[
21]
workers, an LDA-mediated “halogen-dance” isomerized 6 to the
C3-brominated thienoindole 7. The critical central thioether
fragment was constructed using a Pd-catalyzed Stille reaction
S
S
1
2
a
b
91
92
[
21b,22]
N
H
N
using the conditions reported by Kosugi and co-workers.
nC12H25
H
H
Br
H
S
N
S
S
S
NBS, DMF
LDA, THF
R1
R1
N
N
N
H
R2
R2
5
7
6
O
SiMe3
H
(nBu
3
Sn)
2
S
S
S
S
S
S
(0.5 equiv)
R1
R1
R
1
S
3
4
c
90
66
Br
Pd(PPh3)4
(5 mol %)
N
R2
N
R2
N
R2
N
H
N
8
nPr
PhMe, reflux
S
S
Scheme 3. Dimerization to form thioether 8.
d
N
H
N
iPr
The final challenge was construction of the C–C bond to
assemble the central thiophene ring (Scheme 4). The most
common way to install this bond is through iterative deprotonation
S
S
N
of the α-protons on the thiophene moieties followed by
5
e
64
[16a, 23]
subsequent oxidation using CuCl
2
.
This strategy, however,
N
H
produced only decomposition. Optimization by varying the
identity of the base, molarity or copper species did not result in a
positive outcome. We attribute our negative results to the
increased instability of the diionized reactive intermediate in
nBu
S
S
MeO
MeO
MeO
MeO
[24]
comparison to the success cases in the literature. Recently,
6
7
8
f
85
92
84
N
H
N
nC12H25
Attempted oxidative coupling
S
S
i. nBuLi (2.2 equiv)
S
S
N
F
F
THF
decomposition
S
g
h
N
N
ii. CuCl2 (x equiv)
N
nC12H25 8a nC12H25
H
nC12
H
25
Ullman coupling success
S
S
Br Br
S
S
NBS
Cu(0) powder
N
F3C
N
(
2.2 equiv)
(1.5 equiv)
F3C
8a
1a
S
H
nC12H25
DMF
65%
N
N
nC12H25 9a nC12H25
[
a] Isolated after silica gel chromatography.
Scheme 4. Ullman Coupling to form N-heteroacenes.
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Br
Br
Paradies and co-workers have reported that this bond can be
formed to produce a dithienothiophene through a Pd-catalyzed
S
S
NBS
2.2 equiv)
S
S
(
[
25]
dihydro C–H bond coupling reaction. Unfortunately, using their
conditions only decomposition products were recovered.
Successful formation of the central thiophene ring was only
N
S
N
DMF
N
S
N
(2)
nC12H
25
nC12H25
90%
nC12H
25
nC12H25
1
a
1i
[
26]
realized in our system using an Ullman coupling reaction. The
requisite dibromide 9 was generated in situ through the addition
of 2.2 equivalents of N-bromosuccinimide in dimethylform-
Solution-state properties of N-heteroacenes
Optical absorption and cyclic voltammetry measurements were
performed to study the photophysical and electrochemical
[
27]
amide. After two hours, 1.5 equivalents of copper powder (+45
µm particle size) was added and the resulting mixture was heated
to reflux for 16 hours to produce N-heteroheptacene 1a in 65%
[
30]
properties of the N-heteroheptacenes (Table 3, Figure 1).
Despite their different N-substituents, little variation was observed
in the properties of heteroacenes 1a – 1e (entries 1 – 5). All
systems showed similar absorption properties with a λmax at 380
nm and a broad peak at approximately 390 nm (Figure 1a).
Based on the similar appearance of these optical spectra to
related ladder heteroacenes, the peak at 380 nm is tentatively
assigned to a π-π* transition and the lower energy peak to a
[
26],[28]
yield from 8a.
Any deviation from these conditions led to a
significant deleterious effect on the reaction outcome. In line with
our hypothesis, bisdodecyl substituted N-heteroheptacene 1a
was highly soluble in organic solvents. Its solubility in toluene—a
common solvent for ink jet printing—was 26 mg/mL (25 °C, 120
mg/mL at 60 °C).
Using these optimized conditions, the central thiophene ring
was installed in the other thioethers 8b – 8h (Scheme 5). We
found that changing the identity of the N-substituent had a
detrimental effect on the yield of acene formation. In contrast,
changing the electronic nature of the thienoindole had little impact
on the yield of thiophene formation. Irrespective of whether an
electron-donating- or electron-withdrawing substituent was
present, the yield was consistently around 70%.
a
1
.9
.8
0
0
0.7
0
0
0
.6
.5
.4
The solubility of N-heteroheptacene 1a enabled further
functionalization (eq 2). Exposure of it to an excess of N-
bromosuccimide smoothly produced N-heteroacene 1i as a single
0.3
[
29]
regioisomer. With a focused library of N- heteroheptacenes 1a
1i in hand, our attention turned to examining their bulk
properties in solution.
0
0
.2
.1
0
–
2
50
275
300
325
350
375
400
425
450
Wavelength (nm)
1g
S
S
R1
S
S
R1
1
a
1f
1h
1i
i. NBS
R1
R1
S
N
N
R2
ii. Cu(0)
N
R2
S
N
R2
0
.03
R2
b
8
1
0
.025
S
S
S
S
0
.02
N
S
N
N
S
N
Me3Si
SiMe3
nPr
nPr
O
1b, 45%
O
1c, 55%
0.015
0.01
0.005
0
S
S
S
S
N
S
N
N
S
N
iPr
iPr
1
d, 39%
1
e, 55%
-0.5
0
0.5
1
1.5
2
MeO
MeO
OMe
OMe
S
S
nBu
nBu
-0.005
N
S
N
-0.01
F
F
Potential (V)
1g
nC12H25
nC12H25
S
S
1
a
1f
1h
1i
1
f, 70%
N
S
N
S
S
nC12H25
nC12H25
–5
Figure 1. (a) Stacked UV-Vis spectra of 2 × 10 M solutions of N-heterohepta-
F3C
CF3
1g, 72%
cenes 1a, 1f, 1g, 1h, and 1i in CH
2
Cl
10 M solutions of N-heteroheptacenes 1a, 1f, 1g, 1h, and 1i in a 0.1 M
solution of n-Bu NPF in CH Cl using a Pt working electrode with a scan rate
2
. (b) Stacked cyclic voltammograms of 1
N
S
N
–5
×
nC12H25
nC12H25
4
6
2
2
1
h, 72%
–
1
of 50 mV·s
.
Scheme 5. Scope of Ullman coupling to form N-heteroheptacenes.
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Table 3. Photophysical and electrochemical data N-heteroheptacenes.
a
b
onset
c
d
e
entry
#
λ
abs (nm)
E
G
(eV)
E
ox (V)
E
ox
(V)
E
HOMO
E
LUMO
1
2
3
4
5
6
7
8
9
1a
1b
1c
1d
1e
1f
380, 401
377, 396
379, 400
380, 401
379, 399
392, 414
382, 403
383, 407
386, 408
2.92
1.00, 1.72
1.01, 1.66
0.99
0.72
0.79
0.72
0.72
0.78
0.49
0.88
0.95
0.81
–5.03
–5.10
–5.03
–5.03
–5.09
–4.80
–5.19
–5.26
–5.12
–2.11
–2.28
–2.15
–2.13
–2.19
–2.13
–2.31
–2.42
–2.29
2.82
2.88
2.90
2.90
2.77
2.88
2.84
2.83
0.99, 1.60
1.05
0.59, 1.12
1.09, 1.68
1.24
1g
1h
1i
1.07, 1.67
–
5
[
a] Measured in a CH Cl solution (2 × 10 M). [b] Estimated from the onset of absorption [c] Potentials vs Ag/AgCl obtained from cyclic voltammetry: 0.1 M n-
2 2
–1
Bu
4
NPF
6
in CH
2
Cl
2
, Pt as the working electrode with a scan rate of 50 mV·s . The potentials are calibrated with ferrocene as the internal standard. [d] Calculated
using the empirical equation EHOMO = – (Eox
onset
e
+ 4.31). Derived from E
G
and EHOMO
.
[
31]
transition that has some charge-transfer character.
Consequently, these N-heteroheptacenes all display a similar
HOMO-LUMO band gap of approximately 2.90 eV. In contrast,
1
the identity of the indole R -substituent exerted a much larger
influence on both the photophysical and electrochemical
properties of the N-heteroheptacene (entries 1, 6 – 9). While the
trifluromethyl substituent only slightly changed the absorption
peaks of 1h, the dimethoxy substituents shifted the absorption
peaks of 1f by 12 and 13 nm. In comparison to 1a, the dimethoxy-
substituted 1h exhibited a higher EHOMO and ELUMO. These higher
MO energy positions suggested that it would have relatively poor
aerobic stability, which was supported by the empirical
observation that the color of this compound changed from yellow
1
to black upon exposure to air. Replacing the R -hydrogen with an
electron-withdrawing substituent lowered the EHOMO and ELUMO
with the largest drop observed with the bistrifluoromethyl-
substituted heteroacene 1h, in which the positions of the HOMO
and LUMO are lowered by approximately 0.23 and 0.31 eV.
These attenuated positions manifest in the observation of only a
single oxidation peak in the cyclic voltammogram. Despite this
change, the band gap was hardly effected remaining in between
2
.82 and 2.92 eV.
Solid-state properties of N-heteroacenes
Although the identity of the N-substituent did not affect the
solution phase electronic nature of the N-heteroheptacenes, it did
perturb their crystal-packing. While N-heteroacene 1a proved
resistant to crystallization, single crystals of 1d and 1e were
obtained by slow evaporation from a mixture of hexanes and
dichloromethane at room temperature. X-Ray crystallographic
analysis revealed that both N-heteroheptacenes 1d and 1e are
Figure 2. (a) X-Ray crystal structure of N-heteroheptacene 1d (CCDC 1535577).
Hydrogen atoms were removed for clarity.
(b) Packing motif of N-
heteroheptacene 1d. Hydrogen atoms and isopropyl groups were removed for
clarity.
[
32]
planar (Figure 2). N-Isopropyl heteroheptacene 1d packs in an
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FULL PAPER
[
33]
1
–1
–2
edge-face manner, which leads to a herringbone structure. To
minimize the steric effect imposed by the isopropyl substituents,
the antiparallel dimer was only formed with the closed C–C
distance of 3.61 Å. Within one layer, the S···S interaction of 3.62
Å dominates the distance between the dimers. We attribute edge-
face relationship between the layers to the C–H···π interaction of
·s with a capacitance of 2.5 nF·cm and a threshold voltage of
+9 V (Figure 6). This performance underscores that good
transport results from the combination of a uniform film and good
packing. Together with the thienoindole-based N-substituted
[
37]
heteroacenes, the success of the N-dodecyl substituted 1a in a
thin-film field effect transistor encourages future investigation of
this scaffold.
2
.80 Å between a hydrogen atom of the isopropyl group and the
[
34]
backbone of the adjacent molecule.
In comparison to 1d, N-heteroheptacene 1e has a more
complicated crystal structure (Figure 3). This increased
(a)
complexity is attributed to the varying torsional angle of the N-4-
n-butylphenyl-substituent with the crystal. In this crystal, two
molecules form a parallel dimer to obtain a wide intermolecular π-
[
32]
π stacking that exhibits a closest C–C distance of 3.46 Å. While
one molecule shows two parallel aryl groups with a torsional angle
of 51.4° and 56.2° with respect to the acene core, the other
molecule’s aryl groups exhibit torsional angles of 47.1° and 125.9°.
This arrangement may be due to the C–H···π interaction of 3.02
Å between the hydrogen atom (H261) of the aryl group and the π-
[
34]
system of the aryl group in the other molecule. In comparison
to 1d, the shorter distance of 3.40 – 3.42 Å between the dimers
[
17]
indicates that S···S interactions are more significant.
interactions lead to a herringbone packing of N-heteroheptacene
e.
These
(b)
1
OFET device properties of N-heteroacenes
A series of top-gate/bottom-contact thin-film transistors (TFTs,
Figure 4) were fabricated using the N-heteroacenes 1a – 1g. Top-
gate bottom-contact TFTs were fabricated on poly(ethylene)
naphthalate (PEN). Plastic substrates were cleaned in an
ultrasound bath, and a buffer layer of ActivInk B2000 (Polyera
3
.46 Å
3
.40 Å
[
35]
Corporation) was spin-coated and UV-cured. The gold source-
drain contacts (30 nm thick) were deposited by thermal
evaporation to yield channel lengths and widths of 50 µm and 1
mm, respectively. The semiconductor thin films (ca. 40 – 50 nm)
were deposited on untreated Au (S-D contacts)/glass substrates
–
1
by spin-coating the solutions (ca. 5 – 10 mg·mL ). Next, the
Cytop dielectric layer (~1 µM) was spin-coated from polymer
solutions. After mild film annealing at 110 °C in air for 5 min, the
Au-gate electrode was deposited by thermal evaporation. All the
device processing and electrical measurements were performed
in an ambient atmosphere, except for the Au contact vapor
deposition. The field-effect mobilities µ were calculated in the
Figure 3. (a) X-Ray crystal structure of N-heteroheptacene 1e (CCDC 1535588).
Hydrogen atoms and n-butyl groups removed for clarity. (b) Packing motif of N-
heteroheptacene 1e. Hydrogen atoms and n-butylphenyl groups removed for
clarity.
i
saturation region by using the equation µ = (2ISDL)/[WC(VSG –
Au
Cytop dielectric
2
V
th) ]; where ISD = saturation current, L = channel length, W =
channel width, VSG = gate voltage, and Vth = threshold voltage.
In preliminary experiments, the charge transport of these
heteroacenes were investigated in thin film transistor
N-heteroacene
Au*
Au*
Activlnk B2000™
Glass
a
architecture. Among the new N-heteroacenes, only 1a afforded a
uniform film morphology when the semiconductor thin film was
[
36]
Figure 4. Structure of the bottom-contact top-gate thin film transistor used in
this study.
processed with dichlorobenzene as the solvent. Atomic force
microscopy, however, showed that this film was poorly textured
(
Figure 5), and an X-ray diffractogram of the film did not show any
significant reflections. In contrast, the other semiconductors were
rough with disconnected grains. Consequently, only
2
–
semiconductor 1a showed hole-transport mobility of 0.02 cm ·V
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201701966
FULL PAPER
Fujian Hundred Talents Plan for their generous financial support.
AF
thanks
the
Shenzhen
Peacock
Plan
project
(
KQTD20140630110339343). We thank Mr. Furong Sun (UIUC)
for high resolution mass spectrometry data.
Keywords: N-heteroacene • C–H bond amination • nitrene •
rhodium • field effect transistor
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Acknowledgments
[
We are grateful to the National Science Foundation (CHE-
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Chemistry - A European Journal
10.1002/chem.201701966
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A series of N-heteroheptacenes was
F. Zhou, S. Liu, B. D. Santarsiero, D. J.
Wink, D. Boudinet, A. Facchetti and T.
G. Driver*
synthesized from ortho-thiophene-
II
substituted aryl azides using a Rh
2
-
catalyzed C–H bond amination
reaction. The solution- and solid-state
properties are reported.
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Synthesis and Properties of New N-
Heteroheptacenes for Solution-Based
Organic Field Effect Transistors
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