Trifluoromethylation of Anthraquinones for n-Type Organic Semiconductors in Field Effect Transistors

Article abstract of DOI:10.1021/acs.joc.9b01263

This study puts forth a new design of n-type organic semiconductors, which has trifluoromethylethynyl groups attached to 9,10-anthraquinone at different positions. These electron-deficient anthraquinones are synthesized by trifluoromethylation of the corresponding trimethylsilyl-protected alkynes with fluoroform-derived CuCF₃, and their ?-πstacking in the crystals is tunable by varying the positions of trifluoromethylethynyl groups. It is found that most of these trifluoromethylated anthraquinones function as n-type semiconductors in solution-processed field effect transistors with electron mobility of up to 0.28 cm² V^-1 s^-1

Full text of DOI:10.1021/acs.joc.9b01263

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Article
Trifluoromethylation of Anthraquinones for n-Type
Organic Semiconductors in Field Effect Transistors
Mengna Zhao, Xinkan Yang, Gavin Chit Tsui, and Qian Miao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01263 • Publication Date (Web): 16 Jul 2019
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Trifluoromethylation of Anthraquinones for n-Type Organic Semiconductors in Field
Effect Transistors
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Mengna Zhao, Xinkan Yang, Gavin Chit Tsui*, Qian Miao*
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories,
Hong Kong, China
*
gctsui@cuhk.edu.hk, miaoqian@cuhk.edu.hk
Abstract
This study puts forth a new design of n-type organic semiconductors, which has
trifluoromethylethynyl groups attached to 9,10-anthraquinone at different positions. These
electron-deficient anthraquinones are synthesized by trifluoromethylation of the
corresponding trimethylsilyl-protected alkynes with fluoroform-derived CuCF , and their π-π
3
stacking in the crystals is tunable by varying the positions of trifluoromethylethynyl groups.
It is found that most of these trifluoromethylated anthraquinones function as n-type
semiconductors in solution-processed field effect transistors with electron mobility of up to
2
−1 −1
0
.28 cm V s .
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Introduction
Herein we demonstrate that trifluoromethylation of anthraquinone derivatives results
in novel n-type organic semiconductors, which exhibit field effect mobility of up to 0.28
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cm /Vs in solution-processed organic field effect transistors (OFETs). OFETs are one of the
most important elemental devices of organic semiconductors for a variety of applications in
light-weight, low-cost, flexible and wearable electronics.1 Low-power complementary
circuits require both p- and n-channel OFETs as elemental units, which are based on p- and
n-type organic semiconductors, respectively. Despite recent significant progress in n-channel
2
2
3, 4,
5
OFETs
with field effect mobility exceeding 10 cm /Vs,
n-type organic
6
semiconductors are still underdeveloped in comparison to their p-type counterparts, partially
due to the inherent instability of organic anions, particularly, in the presence of air and water.
When developing new n-type organic semiconductors that combine high field effect mobility,
robust environmental stability and easy processability, one challenge is that only a handful of
electron-deficient π-building blocks are available for molecular design and even fewer have
been demonstrated to lead to high-mobility n-channel OFETs. 7 To meet this challenge, we
explored a new design for n-type semiconductors in this study by attaching trifluoromethyl
groups to 9,10-anthraquinone through an ethynyl linker. Quinones are well known electron
acceptors in organic synthesis and biological systems, but have been rarely explored for
development of n-type organic semiconductors. 8, 9, 10 Trifluoromethyl was used as an
electron-withdrawing substituent for developing n-type organic semiconductors, where
4
-trifluomethylphenyl groups were attached to π-backbones.9, 10, 11 The lowest unoccupied
molecular orbital (LUMO) energy level of 9,10-anthraquninone is calculated as −3.22 eV. As
found from this study, attachment of two trifluoromethylethynyl groups to
9
,10-anthraquinone at different positions can not only lower the calculated LUMO energy
level significantly to −3.82 ~ −3.96 eV but also tune molecular packing in the solid state,
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which is of key importance to charge transport in organic semiconductors. Detailed below are
the
synthesis,
molecular
packing
and
solution-processed
OFETs
of
trifluoromethylethynylated anthraquinones 1a–d (Figure 1).
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Figure 1 Bis(trifluoromethylethynyl)-9,10-anthraquinones (1a–d) with the LUMO energy
levels, which are calculated at the B3LYP level of density functional theory (DFT) with the
6
-311++G(d,p) basis set.
Results and Discussion
Scheme 1 shows the synthesis of 1a from 2,5-dibromo-9,10-anthraquinone (2a) 12 in
1
3
four steps. Reduction of 2a with sodium dithionite followed by methylation
gave
2
,5-dibromo-9,10-dimethoxyanthracene (3a), and the Sonogashira coupling of 3a with
trimethylsilylacetylene gave diethynylated anthracene 4a in a yield of 88%. Subsequent
1
4
using the reported method 15 enabled
reaction of 4a with fluoroform-derived CuCF3
trifluoromethylation of the trimethylsilyl-protected alkynes to afford 5a in a yield of 59%.
Final oxidation of 5a by NBS 16 resulted in trifluomethylated anthraquinone 1a in a yield of
9
5%. In contrast, our attempts to trifluoromethylate anthraquinone 6 with fluoroform-derived
CuCF using the same procedure only gave a trace amount of 1a, which was identified with
3
1
19
H and F NMR. This failure is presumably related to the electron-deficient nature of 6. In a
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similar way, other trifluoromethylated anthraquinones (1b–d) were synthesized in four steps
from the corresponding dihalo-9,10-anthraquinones as shown in Scheme S1–3 in the
Supporting Information.
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Scheme 1 Synthesis of 1a
Reagents and conditions: (a) Na S O , NaOH, tetrabutylammonium bromide, CH I, CH Cl ,
2
2
4
3
2
2
H O; (b) trimethylsilylacetylene, Pd(PPh ) ,CuI, diisopropylamine, THF, reflux; (c) [CuCF ],
2
3 4
3
TMEDA, DMF; (d) NBS, THF, H O.
2
The electrochemical and optical properties of 1a–d, in comparison with those of
,10-anthraquinone (AQ), were studied with cyclic voltammetry (CV) and UV‐vis absorption
9
spectroscopy, respectively. In the test window of CV, 1a–d all exhibited two quasi-reversible
reduction waves but did not exhibit any oxidation waves. Figure 2 compares the cyclic
voltammograms of 1a and AQ, and Figure S1 in the Supporting Information shows the cyclic
voltammograms of 1b–d. As shown in Table 1, the first reduction waves of 1a–d have
half-wave potentials in the range of −1.20 V to −1.11 V versus ferrocenium/ferrocene
+
(
Fc /Fc), which are more positive than that of AQ by 0.23 V to 0.32 V. In comparison to 1a,
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,6‐bis(4-(trifluoromethyl)phenyl)‐9,10‐anthraquinone was reported to have a half-wave
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reduction potential of −0.88 V versus SCE, which is equivalent to −1.28 V versus Fc /Fc.
This indicates that trifluoromethylethynyl is more effective than 4-(trifluoromethyl)phenyl in
lowering LUMO energy level of anthraquinone presumably due to the extra
electron-withdrawing ability of sp carbons in the ethynyl group. On the basis of the first
reduction potentials, the LUMO energy levels of 1a–d are estimated as −3.90 eV to −3.99
eV,17 in good agreement with the DFT calculated values. Quinones 1a–d are all pale-yellow
solids, which form essentially colorless solutions in CH Cl . The solutions of 1a–c in CH Cl
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exhibit very similar absorption spectra with three sets of absorption band in the UV region,
while the absorption band of 1d is broader and less structured with a slightly red-shifted
absorption edge as shown in Figure S2 in the Supporting Information. On the basis of the
absorption edge, the optical gaps of 1a–d are estimated as wide as 3.28 to 3.43 eV. The fact
that 1a–c have essentially the same LUMO energy levels and 1d has a slightly higher LUMO
energy level indicates that the substitution position of trifluoromethylethynyl groups plays a
very minor role in withdrawing electrons from the anthraquinone backbone.
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Table 1 The electrochemical and optical properties of anthraquinones.
Experimental
Calculated
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2
E
red
E
red
LUMO
λedge LUMO HOMO
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V) a
(V) a
(eV) b
(nm) c
(eV) d
(eV) d
(
1
a
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−1.11 −1.57 −3.99
−1.12 −1.67 −3.98
−1.20 −1.72 −3.90
−1.43 −1.84 −3.67
361
369
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−3.96 −7.82
−3.96 −7.83
−3.95 −7.83
−3.82 −7.67
−3.22 −7.41
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1d
AQ
+
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a. Half-wave potential versus Fc /Fc. b. Estimated from LUMO = −5.10 − E
(eV). c.
red
−
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absorption edge from a 1×10 M solution in CH Cl . d. Calculated at the B3LYP level of
2
2
DFT with 6-311++G(d, p) basis set.
Figure 2 Cyclic voltammograms of 1a and 9,10-anthraquinone (AQ) recorded in CH Cl
2
2
+
with Fc / Fc as the internal standard.
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Figure 3 Crystal structure of 1a: (a) brickwork arrangement; (b) π-overlap (the top molecule
is shown in light blue and the bottom molecules are shown in light yellow); (c) weak
hydrogen bonds. (C and O atoms are shown as ellipsoids at the 50% probability level; the
trifluoromethylethynyl substituents in (a) are shown as sticks; and hydrogen atoms in (a) and
(b) are removed for clarity.)
Single crystals of 1a, 1c and 1d qualified for X-ray crystallography were obtained by
slow diffusion of ethyl acetate vapor into the solution in chloroform, while the crystals of 1b
obtained with the same method had low quality. Figure 3a shows the crystal structure of 1a,
where molecules of 1a are packed in a brickwork arrangement as viewed along the long axis
of anthraquinone. Each molecule is stacked with four adjacent molecules with two different
π-π distances, 3.12 and 3.55 Å. As shown in Figure 3b, the π-overlap between molecules M1
and M6, which have a smaller π-π distance, occurs mainly between the carbonyl groups and
results in three intermolecular C-C contacts as short as 3.46 to 3.50 Å between the edges of
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anthraquinone. The π-overlap between molecules M1 and M7 occurs between the edges of
anthraquinone as well as ethynyl groups, resulting in four intermolecular C-C contacts of
3.54 to 3.67 Å. As shown in Figure 3c, neighboring π-stacks of 1a are separated by short
H···O contacts (2.40 Å), which are shorter than the sum of the van der Waals radii of H and
O atoms (2.72 Å). This intermolecular H···O contact can be considered as a weak H-bond
since its C-H···O angle (166.0°) is close to 180°.
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Similarly, 1c in crystals also exhibits a brickwork arrangement as viewed along the
long axis of anthraquinone as shown in Figure 4a. However, unlike 1a, the adjacent π-planes
of 1c are not parallel to each other but form a dihedral angle of 13.06°. Each molecule (e.g.
M1) is stacked with four adjacent molecules (e.g. M4, M5, M6 and M7), resulting two
patterns of π-overlap as shown in Figure 4b. The π-overlap between molecules M1 and M6
occurs between the edges of anthraquinone as well as ethynyl groups, resulting in
intermolecular C-C contacts of 3.55 to 3.64 Å. The π-overlap between molecules M1 and M7
occurs mainly between the carbonyl groups and results in three intermolecular C-C contacts
as short as 3.50 to 3.52 Å between the edges of anthraquinone. Similar to 1a, 1c also exhibits
weak H-bonds as shown with dashed red lines in Figure 4c, where the H-to-O distance is 2.46
to 2.48 Å and the C-H···O angle 149.5 to 151.9°.
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Figure 4 Crystal structure of 1c: (a) brickwork arrangement; (b) π-overlap (the top molecule
is shown in light blue and the bottom molecules are shown in light yellow); (c) weak
hydrogen bonds. (C and O atoms are shown as ellipsoids at the 50% probability level; the
trifluoromethylethynyl substituents in (a) are shown as sticks; and hydrogen atoms in (a) and
(b) are removed for clarity.)
Unlike 1a and 1c, 1d exhibits one-dimensional π-π stacking with two slightly
different π-π distances, 3.46 and 3.52 Å, as shown in Figure 5a. The two molecules of 1d
separated by 3.52 Å (e.g. M4 and M5) exhibit larger overlap than those separated by 3.46 Å
(e.g. M1 and M2) as shown in Figure 5b. Weak H-bonds similar to those of 1a and 1c are not
found in the crystal structure of 1d. The crystal structures of 1a, 1c and 1d indicate that
varying the positions of two trifluoromethylethynyl groups that attached to
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,10-anthraquinone enables fine tuning of the π-stacking motifs, in particular, the degree of
π-overlap, in the crystals.
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Figure 5 Crystal structure of 1d: (a) 1D π-stacking as viewed along the b axis; (b) π-overlap
(the top molecule is shown in light blue and the bottom molecules are shown in light yellow).
(C and O atoms are shown as ellipsoids at the 50% probability level; the
trifluoromethylethynyl substituents in (a) are shown as sticks; and hydrogen atoms are
removed for clarity).
The low-lying LUMO energy levels and π-π interactions found in the single crystals
suggest that 1a–d can function as n-type organic semiconductors in the solid state. To test
their potential semiconductor properties in OFETs, thin films of 1a–d were deposited by two
solution-based methods, namely, drop-casting and dip-coating, onto a silicon substrate, which
had
successive
layers
of
thermally
grown
silica,
alumina,
and
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2-cyclohexyldodecylphosphonic acid (CDPA) as a composite dielectric material. Here,
CDPA formed a self-assembled monolayer (SAM) on alumina to passivate surface hydroxyl
groups and to provide an ordered dielectric surface wettable by common organic solvents 18
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and the resulting CDPA-AlO /SiO had a capacitance per unit area (Ci) of 26 ± 1 nF/cm . It
x
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was found that dip-coating resulted in better films of 1a and 1b, while drop-casting resulted
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in better films of 1c and 1d. As observed from polarized-light micrographs and atomic force
micrographs shown in Figure S7 and S8 (Supporting Information), 1a formed isolated
crystals larger than 0.2 mm×0.1 mm, while 1b–d formed continuous films consisting of
crystalline fibers or ribbons that are about 1 to 10 μm wide. The crystals of 1a are in fact
single crystals as indicated by the fact that rotating the crystal by 45° under cross-polarized
light led to extinction. X-ray diffraction from the film of 1a exhibited a strong peak at 2θ =
1
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2.39˚ (d spacing of 7.15 Å), in accordance with the (002) diffraction as derived from the
single crystal structure as shown in Figure S9 in the Supporting Information. Similarly, the
film of 1c exhibited two diffraction peaks corresponding to the (100) and (200)
crystallographic planes of the single crystal; and the film of 1d exhibited three diffraction
peaks corresponding to the (001), (002) and (003) crystallographic planes of the single crystal.
These diffractions indicate lamellar structures in the films with the corresponding
crystallographic planes parallel to the substrate surface. Therefore, it can be concluded that
1
a, 1c and 1d all favor an edge-on orientation on the surface as shown in Figure S10 in the
Supporting Information. X-ray diffraction from the film of 1b also exhibited two strong at 2θ
9.78° and 24.57°, which indicate an ordered arrangement of molecules in the film but
=
cannot provide information about molecular orientation due to lack of single crystal
structures.
The fabrication of OFETs was completed by depositing a layer of gold on the organic
films through a shadow mask to form top-contact source and drain electrodes. In particular, a
needle-shaped organic crystal 19 was used as the shadow mask for fabricating single-crystal
transistors of 1a. When measured under vacuum, the crystals of 1a and the films of 1b and 1d
all functioned as n-type semiconductors, while the films of 1c were essentially insulating
without field effect. Table 2 summarizes the device performance of 1a–d, and Figure 6 shows
the transfer curve of the best performing device of 1a, from which a field effect mobility of
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.28 cm /Vs for electron is extracted. The fact that 1b and 1d have a lower electron mobility
than 1a can be attributed to the polycrystalline films of 1b and 1d, where charge transport is
limited by grain boundaries. The relatively high mobility of 1a also benefits from a favorable
alignment of molecules on the surface (Figure S10a in the Supporting Information), which
allows the direction of π-π stacking parallel to the surface, although the degree of π-overlap
in the crystals is small. On the other hand, why the films of 1c did not exhibit field effect
remains an unanswered question.
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Table 2 Electron mobility (μ ), on/off ratio (I /I ) and threshold voltage (V ) of OFETs of
e
on off
th
1a–d.a
2
μ
e
(cm /Vs)
.087 ± 0.072
highest: 0.28
.029±0.010
I
on/Ioff
Vth (V)
0
4
5
1
a
24–30
1
0 – 10
0
3
4
1
b
22–26
–
1
0 −10
highest: 0.042
No field effect
1
c
–
.5±2.0×10−4
4
2
3
1
d
24–28
1
0 – 10
highest: 2.1×10−3
a
Electrical measurements were conducted under vacuum and data collected from more than
0 channels on more than 6 substrates for each compound.
3
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Figure 6 Transfer curve for the best-performing OFET of 1a on CDPA-modified substrates
measured under vacuum with a photograph for the device (channel width: 670 µm, channel
length: 24 µm).
Conclusion
In summary, four trifluoromethylethynylated anthraquinones (1a–d) were designed as
new n-type organic semiconductors and synthesized by trifluoromethylation of the
corresponding trimethylsilyl-protected alkynes with fluoroform-derived CuCF . It is found
3
that their π-π stacking in the crystals is tunable by varying the positions of
trifluoromethylethynyl groups. These trifluoromethylated anthraquinones except 1c all
behaved as n-type semiconductors in solution-processed field effect transistors, and 1a
exhibited electron mobility of up to 0.28 cm V s−1. This study suggests that late-stage
trifluoromethylation is a promising way to develop novel n-type semiconductors.
Experimental Section
2
−1
Synthesis
General: The reagents and starting materials employed were commercially available and
used without any further purification if not specified elsewhere. Anhydrous and O -free THF
2
and CH Cl were purified by an Advanced Technology Pure-Solv PS-MD-4 system. For
2
2
1
reactions that required heating, the heat source was oil bath. H-NMR (400 MHz),
1
3
C{ H}-NMR (100 MHz) or 19F-NMR (376 MHz) spectra were recorded on a Brucker
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AVANCE III spectrometer. Chemical shift values (δ) are expressed in parts per million using
1
13
1
residual solvent peaks ( H-NMR, δ = 7.26 for CDCl ; C{ H}-NMR, δ = 77.16 for CDCl )
H
3
C
3
1
9
as internal reference. Chemical shifts of F-NMR are reported using benzotrifluoride (−63.72
ppm) as internal standard. Mass spectra were recorded on a Thermo Finnigan MAT 95 XL
spectrometer, Bruker 9.4T FTICR MS (solarix) spectrometer, or Bruker Autoflex speed
MALDI-TOF MS spectrometer. Melting points were measured using a Nikon Polarizing
Microscope ECLIPSE 50i POL equipped with an INTEC HCS302 heating stage without
calibration.
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,6-Dibromo-9,10-dimethoxyanthracene (3a) 13
1
2
2,6-Dibromo-9,10-anthraquinone (2a)
(400 mg, 1.1 mmol, 1 eq) and
tetrabutylammonium bromide (354 mg, 1.1 mmol, 1 eq) were dissolved in 15 mL of CH Cl .
2
2
To this solution was added a solution of Na S O (432 mg, 2.48 mmol, 2.25 eq) and 1.5 g of
2
2
4
NaOH in 7.5 mL of water under an atmosphere of N , and the resulting mixture was stirred
2
for 2 h at room temperature. After slow addition of methyl iodide (0.7 mL, 11 mmol, 10 eq)
via a syringe, the mixture was stirred at room temperature under an atmosphere of N for
2
another 8 h and then extracted with CH Cl . The combined organic layers were washed with
2
2
water and brine, dried over anhydrous Na SO , and concentrated under reduced pressure. The
2
4
product was purified by column chromatography using hexane/CH Cl (4/1, v/v) as the eluent,
2
2
1
yielding 275 mg (0.70 mmol, 64%) of 3a as a yellow solid. H-NMR (400 MHz, CDCl ): δ =
3
4
3
3
8.43 (d, J(H, H) = 1.6 Hz, 2H), 8.16 (d, J(H, H) = 9.2 Hz, 2H), 7.57 (dd, J(H, H) = 9.2 Hz,
4
1
13
J(H, H) = 2 Hz, 2H), 4.09 (s, 6H) ppm. The H-NMR data are consistent with the reported.
,6-Bis((trimethylsilyl)ethynyl)-9,10-dimethoxyanthracene (4a)
To a suspension of 3a (200 mg, 0.50 mmol, 1 eq), Pd(PPh ) (58 mg, 0.05 mmol, 0.1
2
3
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eq) and CuI (19 mg, 0.10 mmol, 0.2 eq) in 10 mL of diisopropylamine (dried over molecular
sieve 4Å) and 10 mL of THF was added trimethylsilylacetylene (0.28 mL, 2 mmol, 4 eq)
under a nitrogen atmosphere at room temperature. The mixture was heated to 80 °C and
stirred overnight. After cooled to room temperature, the mixture was filtered through a short
pad of celite, and the filtrate was concentrated under reduced pressure. The residue was
purified by column chromatography using hexane/CH Cl (4/1, v/v) as the eluent, yielding
1
1
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1
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1
1
90 mg (0.44 mmol, 88%) of 4a as a yellow solid. m.p.: 232–234 ºC. H‐NMR (400 MHz,
3
3
4
CDCl ): δ = 8.40 (s, 2H), 8.20 (d, J(H, H) = 9.2 Hz, 2H), 7.49 (dd, J(H, H) = 8.8 Hz, J(H,
3
1
3
1
H) = 1.6 Hz, 2H), 4.09 (s, 6H), 0.31(s, 18H) ppm; C{ H}-NMR (100 MHz, CDCl ): δ =
3
1
44.8, 128.2, 127.1, 125.2, 124.4, 122.9, 120.5, 105.8, 95.9, 63.8, 0.2 ppm; HRMS‐ESI+
+
(m/z): calcd. for C H O Si [M] 430.1778; found, 430.1778.
2
6
30
2
2
2
,6‐Bis((trifluoromethyl)ethynyl)‐9,10‐dimethoxyanthracene (5a)
To a test tube equipped with a magnetic stir bar was added 4a (172 mg, 0.4 mmol, 1
eq), 8 mL DMF, TMEDA (360 μL, 2.4 mmol, 6 eq.) and a 0.5 M solution (4.8 mL, 6 eq.) of
CuCF in DMF, which was prepared from CHF and CuCl following the reported procedure
3
3
1
5
(Method B). The reaction mixture was stirred in air at room temperature for 18 h, then
diluted with diethyl ether (5 mL) and poured into 250 mL ice water. After stirring for 30 min,
the mixture was filtered and the solid was washed with water. The crude product was purified
by column chromatography using hexane/CH Cl (4/1, v/v) as the eluent, yielding 100 mg
2
2
1
(
0.24 mmol, 59%) of 5a as a yellow solid. m.p.: 249–250 ºC. H-NMR (400 MHz, CDCl ): δ
3
3
3
4
= 8.59 (s, 2H), 8.32 (d, J(H, H) = 9.2 Hz, 2H), 7.56 (dd, J(H, H) = 8.8 Hz, J(H, H) = 1.2
Hz, 2H), 4.14 (s, 6H) ppm; 13C{ H}-NMR was not recorded due to its low solubility;
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+
F-NMR (376 MHz, CDCl ): δ = −50.7 (s, 3F) ppm; HRMS‐ESI (m/z): calcd. for
3
+
C H F O [M] 422.0736; found, 422.0737.
2
2
12
6
2
2
,6‐Bis((trifluoromethyl)ethynyl)‐9,10‐anthraquinone (1a)
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To a stirred solution of 5a (50 mg, 0.12 mmol, 1 eq) in anhydrous THF (40 mL) was
added an aqueous solution (3 mL) of NBS (428 mg, 2.4 mmol, 20 eq) under a nitrogen
atmosphere at room temperature. The mixture was stirred at room temperature for 30 min and
then extracted with diethyl ether. The combined organic layers were washed with water and
brine, dried over anhydrous Na SO , and concentrated under reduced pressure to give almost
2
4
pure product. Further purification by recrystallization from acetone gave 45 mg (0.11 mmol,
1
9
5%) of 1a as a yellow solid. m.p.: 188–190 ºC. H‐NMR (400 MHz, CDCl ): δ = 8.52 (d,
3
4
3
3
4
J(H, H) = 1.6 Hz, 2H), 8.39 (d, J(H, H) = 8 Hz, 2H), 8.0 (dd, J(H, H) = 8 Hz, J(H, H) =
1
3
1
19
1
.6 Hz, 2H) ppm; C{ H}-NMR was not recorded due to its low solubility; F‐NMR (376
+
+
MHz, CDCl ): δ = −51.5 (s, 3F) ppm. HRMS‐ESI (m/z): calcd. for C H F O [M]
3
20
6
6
2
392.0267; found, 392.0271.
2
,7-Dibromo-9,10-dimethoxyanthracene (3b)
2,7-Dibromo-9,10-anthraquinone (2b)20 (250 mg, 0.68 mmol, 1 eq) and
tetrabutylammonium bromide (219 mg, 0.68 mmol, 1 eq) were dissolved in 20 mL of CH Cl .
2
2
To this solution was added a solution of Na S O (268 mg, 1.54 mmol, 2.25 eq) and 1g of
2
2
4
NaOH in 5 mL of water under an atmosphere of N , and the resulting mixture was stirred for
2
2
h at room temperature. After slow addition of methyl iodide (0.42 mL, 6.8 mmol, 10 eq) via
a syringe, the mixture was stirred at room temperature under an atmosphere of N for another
2
8
h and then extracted with CH Cl . The combined organic layers were washed with water
2 2
and brine, dried over anhydrous Na SO , and concentrated under reduced pressure. The
2
4
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product was purified by column chromatography using hexane/CH Cl (4/1, v/v) as the eluent,
2
2
1
yielding 147 mg (0.37 mmol, 54%) of 3b as a yellow solid. m.p.: 207–208 ºC. H-NMR (400
4
3
MHz, CDCl ): δ = 8.44 (d, J(H, H) = 1.6 Hz, 2H), 8.15 (d, J(H, H) = 9.2 Hz, 2H), 7.56 (dd,
3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
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3
4
13
1
J(H, H) = 9.2 Hz, J(H, H) = 2 Hz, 2H), 4.10 (s, 3H), 4.09 (s, 3H) ppm; C{ H}-NMR (100
MHz, CDCl ): δ = 149.4, 146.8, 129.4, 126.5, 124.8, 124.8, 123.5, 121.0, 63.8, 63.7 ppm;
3
+
+
HRMS-ESI (m/z): calcd. for C H Br O [M] 395.9178; found, 395.9172.
16 12
2
2
2
,7-Bis((trimethylsilyl)ethynyl)-9,10-dimethoxyanthracene (4b)
To a suspension of 3b (120 mg, 0.3 mmol, 1 eq), Pd(PPh ) (35 mg, 0.03 mmol, 0.1
3
4
eq) and CuI (11 mg, 0.06 mmol, 0.2 eq) in 6 mL of diisopropylamine (dried over molecular
sieve 4Å) and 6 mL of THF was added trimethylsilylacetylene (0.18 mL, 1.2 mmol, 4 eq)
under a nitrogen atmosphere at room temperature. The mixture was kept under the nitrogen
atmosphere and stirred at 80 °C overnight, then cooled to room temperature, and filtered
through a short pad of celite. The filtrate was concentrated under reduced pressure. The
residue was purified by column chromatography using hexane/CH Cl (4/1, v/v) as the eluent,
2
2
1
yielding 120 mg (0.28 mmol, 93%) of 4b as a yellow solid. m.p.: 193–194 ºC. H-NMR (400
3
3
MHz, CDCl ): δ = 8.42 (s, 2H), 8.20 (d, J(H, H) = 9 Hz, 2H), 7.50 (d, J(H, H) = 8.9 Hz,
3
1
3
1
2
1
H), 4.13 (s, 3H), 4.08 (s, 3H), 0.31 (s, 18H) ppm; C{ H}-NMR (100 MHz, CDCl ): δ =
3
48.5, 148.4, 128.2, 127.1, 124.8, 124.6, 122.8, 120.2, 105.6, 95.6, 63.9, 63.4, 0.02 ppm;
+
+
HRMS-ESI (m/z): calcd. for C H O Si [M] 430.1779; found, 430.1778.
26 30
2
2
2,7-Bis((trifluoromethyl)ethynyl)-9,10-dimethoxyanthracene (5b)
To a test tube equipped with a magnetic stir bar was added 4b (86 mg, 0.2 mmol, 1
eq), 4 mL DMF, TMEDA (180 μL, 1.2 mmol, 6 eq) and a 0.5 M solution (2.4 mL, 6 eq.) of
CuCF in DMF, which was prepared from CHF and CuCl following the reported procedure
3
3
15
(
Method B). The mixture was stirred in air at room temperature for 18 h, then diluted with
diethyl ether (2 mL) and poured into 100 mL of ice water. After stirring for 30 min, the
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mixture was filtered and the solid was washed with water. The crude product was purified by
column chromatography using hexane/CH Cl (4/1, v/v) as the eluent, yielding 35 mg (0.083
2
2
1
mmol, 42%) of 5b as a yellow solid. m.p.: 209–210 ºC. H-NMR (400 MHz, CDCl ): δ =
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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2
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7
.58 (s, 2H), 8.31 (d, J(H, H) = 8.8 Hz, 2H), 7.56 (dd, J(H, H) = 9.2 Hz, J(H, H) = 1.6 Hz,
1
3
1
H), 4.16 (s, 3H), 4.11 (s, 3H) ppm; C{ H}-NMR (100 MHz, CDCl ): δ = 149.8, 148.9,
3
29.6, 127.5, 126.0, 124.7, 123.7, 118.8 (q, JCF = 255.1 Hz), 116.2, 86.9 (q, JCF = 6.2 Hz),
1
9
7.4 (q, J = 52.8 Hz), 64.6, 63.8 ppm; F-NMR (376 MHz, CDCl ): δ = −51.0 (s, 3F) ppm.
CF
3
+
+
HRMS-ESI (m/z): calcd. for C H F O [M] 422.0736; found, 422.0739.
2
2
12
6
2
2
,7-Bis((trifluoromethyl)ethynyl)-9,10-anthraquinone (1b)
To a stirred solution of 5b (35 mg, 0.081 mmol, 1 eq) in anhydrous THF (40 mL) was
added an aqueous solution (2 mL) of (NH ) Ce(NO ) (132 mg, 0.24 mmol, 3 eq.) under a
4
2
3 6
nitrogen atmosphere at 0 °C. The mixture was allowed to warm slowly to room temperature
and stirred for 30 min. Extracted with diethyl ether, and then the combined organic layers
were washed with water and brine, dried over anhydrous Na SO , and concentrated under
2
4
reduced pressure to give almost pure product. Further purification was preceded by
recrystallization with acetone to give 30 mg (0.076 mmol, 94%) of 1b as a yellow solid. m.p.:
1
4
3
2
07–208 ºC. H-NMR (400 MHz, CDCl ): δ = 8.53 (d, J(H, H) = 1.2 Hz, 2H), 8.38 (d, J(H,
3
3
4
13
1
H) = 8 Hz, 2H), 8.0 (dd, J(H, H) = 8 Hz, J(H, H) = 1.6 Hz, 2H) ppm; C{ H}-NMR was
1
9
not recorded due to its low solubility; F-NMR (376 MHz, CDCl ): δ = −51.5 (s, 3F) ppm.
3
+
FTICR MS (m/z): calcd. for C H O F [M+H] 393.0345; found, 393.0343.
2
0
7
2 6
2
,3-Dibromo-9,10-anthraquinone (2c)
To a stirred solution of 500 mg (2.1 mmol, 1.2 eq) of 3,4-dibromothiophene (8) and
277 mg (1.75 mmol, 1eq) of 1,4-naphthoquinone (9) in CHCl (10 mL) at 75 ºC was added
3
m-CPBA (70w%, 2.4 g, 9.73 mmol, 5.56 eq) in small portions. After 48 h, the mixture was
cooled and poured into a saturated aqueous solution of Na CO . After the mixture was stirred
2
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for 15 min at room temperature, it was extracted with CH Cl . The combined organic layers
2
2
were washed with water and brine, dried over anhydrous Na SO , and concentrated under
2
4
reduced pressure. The residue was washed with EtOH to give 354 mg (0.97 mmol, 55%) of
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
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4
4
4
4
4
5
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5
5
5
5
5
5
5
6
0
1
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8
9
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9
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6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
3
2
c as a brown solid. H-NMR (400 MHz, CDCl ): δ = 8.53 (s, 2H), 8.33(dd, J(H, H) = 5.6
3
4
3
4
1
Hz, J(H, H) = 3.2 Hz, 2H), 7.86 (dd, J(H, H) = 6 Hz, J(H, H) = 3.6 Hz, 2H) ppm. The H
NMR data are consistent with the reported.21
2
,3-Dibromo-9,10-dimethoxyanthracene (3c)
00 mg (0.82 mmol, 1 eq) of 2,3-dibromo-9,10-anthraquinone (2c) and
3
tetrabutylammonium bromide (264 mg, 0.82 mmol, 1 eq.) were dissolved in 60 mL of
CH Cl . To this solution was added a solution of Na S O (321 mg, 1.84 mmol, 2.25 eq) and
2
2
2
2
4
1
.8 g NaOH in 9 mL of water under an atmosphere of N , and the resulting mixture was
2
stirred for 2 h at room temperature. After slow addition of methyl iodide (0.52 mL, 8.2 mmol,
10 eq) via a syringe, the mixture was stirred at room temperature under an atmosphere of N2
for another 8 h and then extracted with CH Cl . The combined organic layers were washed
2
2
with water and brine, dried over anhydrous Na SO , and concentrated under reduced pressure.
2
4
The product was purified by column chromatography using hexane/CH Cl (4/1, v/v) as the
2
2
eluent, yielding 112 mg (0.26 mmol, 32 %) of 3c as a yellow solid. m.p.: 173–175 ºC.
1
3
4
H-NMR (400 MHz, CDCl ): δ = 8.59 (s, 2H), 8.28 (dd, J(H, H) = 6.8 Hz, J(H, H) = 3.2 Hz,
3
3
4
13
1
2
H), 7.55 (dd, J(H, H) = 6.8 Hz, J(H, H) = 3.6 Hz, 2H), 4.11 (s, 6H) ppm; C{ H}-NMR
(100 MHz, CDCl ): δ = 147.9, 127.4, 126.4, 125.9, 124.3, 122.8, 122.2, 63.8 ppm;
3
+
+
HRMS-ESI (m/z): calcd. for C H Br O [M] 395.9178; found, 395.9184.
1
6
12
2
2
2
,3-Bis((trimethylsilyl)ethynyl)-9,10-dimethoxyanthracene (4c)
To a suspension of 3c (100 mg, 0.25 mmol, 1 eq), Pd(PPh ) (29 mg, 0.025 mmol, 0.1
3
4
eq) and CuI (9.5 mg, 0.05 mmol, 0.2 eq) in 5 mL of dry diisopropylamine and 5 mL of THF
was added trimethylsilylacetylene (0.15 mL, 1 mmol, 4 eq) under a nitrogen atmosphere at
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room temperature. The mixture was heated to 80 °C and stirred overnight. After cooled to
room temperature, was filtered through a short pad of celite, and the filtrate was concentrated
under reduced pressure. The residue was purified by column chromatography using hexane/
CH Cl (4:1) as the eluent, yielding 73 mg (0.17 mmol, 68%) of 4c as a yellow solid. m.p.:
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
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7
8
9
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2
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5
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7
8
9
0
1
2
3
4
5
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8
9
0
1
2
3
4
5
6
7
8
9
0
2
2
1
3
4
2
18–219 ºC. H-NMR (400 MHz, CDCl ): δ = 8.44 (s, 2H), 8.27 (dd, J(H, H) = 6.8 Hz, J(H,
3
3
4
H) = 3.2 Hz, 2H), 7.52 (dd, J(H, H) = 6.8 Hz, J(H, H) = 3.6 Hz, 2H), 4.11 (s, 6H), 0.33 (s,
1
3
1
1
1
4
8H) ppm; C{ H}-NMR (100 MHz, CDCl ): δ = 148.5, 127.9, 126.3, 126.2, 123.3, 123.0,
3
+
+
21.2, 104.0, 98.4, 63.8, 0.3 ppm; HRMS-ESI (m/z): calcd. for C H O Si Na [M+Na]
2
6
30
2
2
53.1676; found, 453.1677.
2,3-Bis((trifluoromethyl)ethynyl)-9,10-dimethoxyanthracene (5c)
To a test tube equipped with a magnetic stir bar was added 4c (64 mg, 0.15 mmol, 1
eq), 3 mL DMF, TMEDA (135 μL, 0.9 mmol, 6 eq) and a 0.5 M solution (1.8 mL, 6 eq.) of
CuCF in DMF, which was prepared from CHF and CuCl following the reported procedure
3
3
15
(
Method B). The reaction mixture was stirred in air at room temperature for 18 h, then
diluted with diethyl ether (2 mL) and poured into 100 mL ice water. After stirring for 30 min,
the mixture was filtered and the solid was washed with water. The crude product was purified
by column chromatography using hexane/CH Cl (4/1, v/v) as the eluent, yielding 35 mg
2
2
1
(
0.083 mmol, 56 %) of 5c as a yellow solid. m.p.: 251–252 ºC. H-NMR (400 MHz, CDCl ):
3
3
4
3
δ = 8.62 (s, 2H), 8.34 (dd, J(H, H) = 6.8 Hz, J(H, H) = 3.2 Hz, 2H), 7.64 (dd, J(H, H) = 6.8
4
13
1
Hz, J(H, H) = 3.2 Hz, 2H), 4.14 (s, 6H) ppm; C{ H}-NMR (100 MHz, CDCl ): δ = 149.5,
3
1
8
30.5, 127.5, 127.4, 123.2, 123.0, 118.7 (q, JCF = 255.8 Hz), 115.8, 84.4 (q, JCF = 6.6 Hz),
1
9
0.4 (q, JCF = 52.8 Hz), 64.2 ppm; F-NMR (376 MHz, CDCl ): δ = −51.2 (s, 3F) ppm.
3
+
+
HRMS-ESI (m/z): calcd. for C H F O [M] 422.0736; found, 422.0731.
2
2
12
6
2
2
,3-Bis((trifluoromethyl)ethynyl)-9,10-anthraquinone (1c)
To a stirred solution of 5c (34 mg, 0.08 mmol, 1 eq) in dry THF (40 mL) was added
2
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an aqueous solution (2 mL) of (NH ) Ce(NO ) (132 mg, 0.24 mmol, 3 eq) under a nitrogen
4
2
3 6
atmosphere at 0 °C. The mixture was allowed to warm slowly to room temperature and
stirred for 30 min. Extracted with diethyl ether, and then the combined organic layers were
washed with water and brine, dried over anhydrous Na SO , and concentrated under reduced
1
1
1
1
1
1
1
1
1
1
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0
1
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8
9
0
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8
9
0
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2
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7
8
9
0
1
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4
5
6
7
8
9
0
1
2
3
4
5
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7
8
9
0
2
4
pressure to give almost pure product. Further purification was preceded by recrystallization
with acetone to give 30 mg (0.077 mmol, 96%) of 1c as a yellow solid. m.p.: 173–174 ºC.
1
3
4
H-NMR (400 MHz, CDCl ): δ = 8.56 (s, 2H), 8.36 (dd, J(H, H) = 5.6 Hz, J(H, H) = 3.2 Hz,
3
3
4
13
1
2
H), 7.90 (dd, J(H, H) = 5.6 Hz, J(H, H) = 3.2 Hz, 2H) ppm; C{ H}-NMR was not
1
9
recorded due to its low solubility; F-NMR (376 MHz, CDCl ): δ = −51.5 (s, 3F) ppm.
3
+
FTICR MS (m/z): calcd. for C H O F [M+H] 393.0345; found, 393.0343.
2
0
7
2 6
1
,5-Dichloro-9,10-dimethoxyanthracene (3d)
(3.6 mmol, eq) of 1,5-dichloro-9,10-anthraquinone (2d) and
tetrabutylammonium bromide (1.16 g, 3.6 mmol, 1 eq) were dissolved in 140 mL CH Cl .
1
g
1
2
2
Na S O (1.4 g, 8.12 mmol, 2.25 eq) dissolved in 5 M NaOH (8 g NaOH in 40 mL water)
2
2
4
was added under an atmosphere of N and the mixture was stirred for 2 h at room temperature.
2
After slow addition of methyl iodide (2.3 mL, 36 mmol, 10 eq) via a syringe, the mixture was
stirred at room temperature under an atmosphere of N for another 8 h and then extracted with
2
CH Cl . The combined organic layers were washed with water and brine, dried over
2
2
anhydrous Na SO , and concentrated under reduced pressure. The product was purified by
2
4
column chromatography using hexane/CH Cl (4/1, v/v) as the eluent, yielding 430 mg (1.4
2
2
1
mmol, 39 %) of 3d as a yellow solid. m.p.: 197–198 ºC. H-NMR (400 MHz, CDCl ): δ =
3
3
3
3
8
.36 (d, J(H, H) = 8.8 Hz, 2H), 7.60 (d, J(H, H) = 7.2 Hz, 2H), 7.40 (dd, J(H, H) = 8.8 Hz,
3
13
1
J(H, H) = 7.2 Hz, 2H), 4.00 (s, 6H) ppm; C{ H}-NMR (100 MHz, CDCl ): δ = 149.1,
3
+
1
29.6, 129.0, 128.9, 125.4, 122.7, 122.5, 64.3 ppm; HRMS-ESI (m/z): calcd. for
+
C H Cl O [M] 306.0209; found, 306.0205.
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,5-Bis((trimethylsilyl)ethynyl)-9,10-dimethoxyanthracene (4d)
Isopropylmagnesium chloride (2 M in THF, 6.5 mL, 13 mmol, 10 eq) and
trimethylsilylacetylene (1.84 mL, 13 mmol, 10 eq) were dissolved in 20 mL dry THF and
heated for 2 h at 60 °C. The resulting solution of [(trimethylsilyl)ethynyl]magnesium bromide
was added dropwise into a stirred solution of 3d (400 mg, 1.3 mmol, 1 eq),
0
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9
0
triphenylphosphine (24 mg, 0.09 mmol, 0.07 eq), and [Ni(acac) ] (23 mg, 0.09 mmol, 0.07 eq)
2
in 40 mL anhydrous THF. The mixture was refluxed for 16 h under a nitrogen atmosphere.
After cooling, the mixture was quenched with NH Cl aqueous, extracted with diethyl ether.
4
Then the combined organic layers were washed with water and brine, dried over anhydrous
Na SO , and concentrated under reduced pressure. The crude product was purified column
2
4
chromatography using hexane/ CH Cl (4/1, v/v) as the eluent, yielding 438 mg (1.01 mmol,
2
2
1
7
8%) of 4d as a yellow solid. m.p.: 207–208 ºC. H-NMR (400 MHz, CDCl ): δ = 8.37 (dd,
3
3
4
3
4
J(H, H) = 8.8 Hz, J(H, H) = 0.8 Hz, 2H), 7.81 (dd, J(H, H) = 6.8 Hz, J(H, H) = 0.8 Hz,
3
3
2
H), 7.44 (dd, J(H, H) = 6.8 Hz, J(H, H) = 8.8 Hz, 2H), 4.04 (s, 6H), 0.35 (s, 18H) ppm;
1
3
1
C{ H}-NMR (100 MHz, CDCl ): δ = 149.6, 135.5, 126.6, 124.9, 124.5, 124.3, 117.8, 106.8,
3
+
+
9
4
1
7.2, 64.4, 0.3 ppm; HRMS-ESI (m/z): calcd. for C H O Si [M] 430.1779; found,
26 30 2 2
+
30.1774; calcd. for C H O Si Na [M+Na] 453.1676; found, 453.1671.
2
6
30
2
2
,5-Bis((trifluoromethyl)ethynyl)-9,10-dimethoxyanthracene (5d)
To a test tube equipped with a magnetic stir bar was added 4d (172 mg, 0.4 mmol, 1
eq), 8 mL DMF, TMEDA (360 μL, 0.9 mmol, 6 eq) and a 0.5 M solution (4.8 mL, 6 eq.) of
CuCF in DMF, which was prepared from CHF and CuCl following the reported procedure
3
3
1
5
(Method B). The reaction mixture was stirred in air at room temperature for 18 h, then
diluted with diethyl ether (5 mL) and poured into 250 mL ice water. After stirring for 30 min,
the mixture was filtered and the solid was washed with water. The crude product was purified
by column chromatography using hexane/CH Cl (4/1, v/v) as the eluent, yielding 58 mg
2
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(
0.14 mmol, 34 %) of 5d as a yellow solid. m.p.: 148–149 ºC. H-NMR (400 MHz, CDCl ): δ
3
3
3
3
=
8.50 (d, J(H, H) = 8.8 Hz, 2H), 7.94 (d, J(H, H) = 6.4 Hz, 2H), 7.56 (dd, J(H, H) = 6.8
3
13
1
Hz, J(H, H) = 8.8 Hz, 2H), 4.07 (s, 6H) ppm; C{ H}-NMR (100 MHz, CDCl ): δ = 149.6,
3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
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3
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4
4
4
4
4
4
4
4
4
5
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5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
7
37.0, 126.7, 126.5, 125.3, 124.4, 119.3 (q, JCF = 254.7 Hz), 113.4, 88.6 (q, JCF = 6.9 Hz),
1
9
9.0 (q, JCF = 51.8 Hz), 64.4 ppm; F-NMR (376 MHz, CDCl ): δ = −50.3 (s, 3F) ppm.
3
+
+
HRMS-ESI (m/z): calcd. for C H F O [M] 422.0736; found, 422.0729.
22 12
6
2
1
,5-Bis((trifluoromethyl)ethynyl)-9,10-anthraquinone (1d)
To a stirred solution of 5d (42 mg, 0.1 mmol, 1 eq) in dry THF (40 mL) was added an
aqueous solution (5 mL) of (NH ) Ce(NO ) (164 mg, 0.3 mmol, 3 eq) under a nitrogen
4 2
3 6
atmosphere at 0 °C. The mixture was allowed to warm slowly to room temperature and
stirred for 30 min, then extracted with diethyl ether. The combined organic layers were
washed with water and brine, dried over MgSO , and concentrated under reduced pressure to
4
give almost pure product. Further purification was preceded by recrystallization with acetone
1
to give 38 mg (0.097 mmol, 97%) of 1d as a yellow solid. m.p.: 195–196 ºC. H-NMR (400
3
4
3
MHz, CDCl ): δ = 8.53 (dd, J(H, H) = 8 Hz, J(H, H) = 1.2 Hz, 2H), 8.04 (d, J(H, H) = 7.6
3
4
3
13
1
Hz, J(H, H) = 1.2 Hz, 2H), 7.89 (t, J(H, H) = 8 Hz, 2H) ppm; C{ H}-NMR was not
1
9
recorded due to its low solubility; F-NMR (376 MHz, CDCl ): δ = −51.2 (s, 3F) ppm.
3
+
FTICR MS (m/z): calcd. for C H O F [M+H] 393.0345; found, 393.0343.
2
0
7
2 6
Cyclic voltammetry. Cyclic voltammetry was performed on a PAR Potentiostat/Galvanostat
Model 263A Electrochemical Station (Princeton Applied Research) at a scan rate of 30
−
1
mVs . All compounds were dissolved in anhydrous CH Cl that contained 0.1 M of
2
2
tetrabutylammonium hexafluorophosphate (Bu NPF ) as the supporting electrolyte. A
4
6
platinum bead was used as a working electrode, a platinum wire was used as an auxiliary
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+
electrode, and a silver wire was used as a pseudo-reference. Ferrocenium/ferrocene (Fc /Fc)
was used as an internal standard.
UV-vis absorption spectra. UV-vis absorption spectra were recorded on a Shimadzu
UV-3600 Plus UV-VIS-NIR spectrophotometer.
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Crystal Structure Determination. The single crystals were grown by diffusion of ethyl
acetate vapor into a solution of chloroform. X-ray crystallography data were collected on a
Bruker AXS Kappa ApexII Duo Diffractometer or Bruker D8 Venture Diffractometer.
DFT calculations. The frontier molecular orbitals were calculated using the Gaussian 09W
software package. The geometries were optimized at the B3LYP level of DFT with the
6
-31G(d,p) basis set, and the molecular orbitals were then calculated with the 6-311++G(d, p)
basis set.
Fabrication and characterization of organic field effect transistors (OFETs)
To fabricate OFETs, the dielectric layer was first formed following the reported
4
method. A solution of Al(NO ) ·9H O in ethanol (0.15 mol/L) was first spin-cast onto a
3
3
2
highly doped silicon substrate, which had a 100 nm-thick layer of SiO on its top. The
2
spin-cast film was then baked at 300 °C for 30 minutes to form a thin layer of aluminum
oxide (Al O ). To modify the Al O layer with a self-assembled monolayer (SAM) of
2
3
2
3
18
1
2-cyclohexyldodecylphosphonic acid (CDPA), the Al O -coated SiO /Si wafer was soaked
2 3 2
in a 0.3 mM solution of CDPA in isopropanol at room temperature for 12 hours, then rinsed
with isopropanol and dried with a flow of nitrogen. The capacitance per unit area (C ) of
i
CDPA-Al O /SiO was measured from a metal-insulator-metal structure, where
2
3
2
vacuum-deposited gold (0.2 mm×1 mm) was the top electrode and the highly doped silicon
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substrate was the bottom electrode, with the frequency ranging from 100 Hz to 100 kHz. As
2
taken at the lowest frequency (100 Hz), the C of CDPA- Al O /SiO is 26 ± 1 nF/cm .
i
2
3
2
Thin films of 1a, 1b were dip-coated on the CDPA-Al O /SiO dielectric by
2
3
2
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immersing the substrate (substrate size: 1.2 cm×0.6 cm) vertically in a solution and then
pulling up at a constant speed with a LongerPump TJ-3A syringe pump. The optimized
conditions for dip coating are: 1a in CH Cl /acetone(3/1, v/v, saturated) with a pulling speed
2
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of 250 μm/min; 1b in CH Cl /acetone (1/1, v/v, 2 mg/mL) with a pulling speed of 200
2
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μm/min. Thin films of 1c, 1d were drop-cast on the CDPA-Al O /SiO dielectric by drop a
2
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solution onto a tilted substrate (three drops, tilt angle = ~5°), which was covered with a glass
dish to allow the solvent to evaporate slowly. The optimized concentrations and solvents are
0.5 mg/mL of 1c in CHCl and 1.0 mg/mL of 1d in CH Cl /acetone (2/1, v/v). Top contact
3
2
2
drain and source gold electrodes were then vacuum-deposited through a shadow mask onto
the organic films using an Edwards Auto 306 vacuum coating system with a Turbomolecular
-6
pump at a pressure of 4.0×10 torr or lower, with a deposition rate of ca. 2 nm/min to the
desired thickness as measured by a quartz crystal sensor.
The current-voltage measurement was carried out on a JANIS ST-500-20-4TX probe
station with a Keithley 4200 Semiconductor Characterization System at room temperature
−4
under vacuum (background pressure of 2.0 × 10 mbar or lower). The field effect mobility
2
was extracted from transfer I-V curve using the equation: I = (μWC /2L) (V –V ) , where
D
i
GS
th
ID is the drain current, μ is field effect mobility, W and L are the effective channel width and
length, respectively, C is the capacitance per unit area for the CDPA-Al O /SiO substrates,
i
2
3
2
V and V are the gate and threshold voltage, respectively. The average field effect mobility
GS
th
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for each compound was obtained from at least 30 channels on more than 6 individual
substrates.
Polarized optical images of the devices were obtained using a Nikon 50IPOL
microscope. The AFM images were collected with a Nanoscope IIIa Multimode Microscope
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(Digital Instruments) using tapping mode and in air under ambient conditions. X-ray
diffraction from thin films were recorded on a SmartLab X-Ray Refractometer.
Supporting Information
Cyclic voltammograms, UV-vis absorption spectra, DFT calculation data,
characterization of thin films and field effect transistors of 1a–d and NMR spectra for all
compounds. Crystallographic data for compound 1a, 1c, 1d.
Acknowledgements
We thank Ms. Hoi Shan Chan (the Chinese University of Hong Kong) for the single
crystal crystallography. Ms. Zhao thanks the Hong Kong PhD Fellowship for financial
support, and G. C. Tusi thanks the Research Grants Council of Hong Kong (CUHK
2
4301217), the Chinese University of Hong Kong (the Faculty Strategic Fund for Research
from the Faculty of Science and the Direct Grant for Research) and the Key Laboratory of
Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Science for research funding.
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