Dinaphthothiepine Bisimide and Its Sulfoxide: Soluble Precursors for Perylene Bisimide

Article abstract of DOI:10.1021/jacs.0c04096

The synthesis and properties of dinaphtho[1,8-bc:1′,8′-ef]thiepine bisimide (DNTBI) and its oxides are described. Their molecular design is conceptually based on the insertion of a sulfur atom into the perylene bisimide (PBI) core. These sulfur-inserted PBI derivatives adopt nonplanar structures, which significantly increases their solubility in common organic solvents. Upon electron injection, light irradiation, or heating, DNTBI and its sulfoxides undergo sulfur extrusion reactions to furnish PBI. The photoinduced and thermal sulfur extrusion reactions proceed almost quantitatively. This unique reactivity enabled the fabrication of a high-performance solution-processed n-type organic field-effect transistor with an electron mobility of up to 0.41 cm2 V-1 s-1.

Full text of DOI:10.1021/jacs.0c04096

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Communication
Dinaphthothiepine Bisimide and Its Sulfoxide:
Soluble Precursors for Perylene Bisimide
Sakiho Hayakawa, Kyohei Matsuo, Hiroko Yamada, Norihito Fukui, and Hiroshi Shinokubo
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c04096 • Publication Date (Web): 16 Jun 2020
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Dinaphthothiepine Bisimide and Its Sulfoxide: Soluble
Precursors for Perylene Bisimide
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Sakiho Hayakawa,† Kyohei Matsuo,‡ Hiroko Yamada,*,‡ Norihito Fukui,*,† and Hiroshi Shinokubo*,†
† Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-
ku, Nagoya, Aichi 464-8603, Japan
‡ Division of Materials Science, Graduate School of Science and Technology, Nara Institute of Science and Technology, 8916-5 Taka-
yama-cho, Ikoma, Nara 630-0192, Japan
ABSTRACT: The synthesis and properties of dinaphtho[1,8-bc:1',8'-ef]thiepine bisimide (DNTBI) and its oxides are described. Their mo-
lecular design is conceptually based on the insertion of a sulfur atom into the perylene bisimide (PBI) core. These sulfur-inserted PBI derivatives
adopt nonplanar structures, which significantly increases their solubility in common organic solvents. Upon electron-injection, light-irradiation,
or heating, DNTBI and its sulfoxides undergo sulfur-extrusion reactions to furnish PBI. The photo-induced and thermal sulfur extrusion reac-
tions proceed almost quantitatively. This unique reactivity enabled the fabrication of a high-performance solution-processed n-type organic
field-effect transistor with an electron mobility of up to 0.41 cm2 V–1 s–1.
Organic semiconductors are key components in organic elec-
tronic and optoelectronic devices.1–5 The use of organic materials as
semiconductors is potentially advantageous considering that large
devices can be fabricated at low cost and/or low temperature based
on solution processes. However, high-performance semiconducting
molecules often exhibit low solubility in organic solvents. The use of
soluble precursors, which provide the corresponding semiconduct-
ing molecules upon appropriate external stimuli such as heat and
light, is a promising approach to solve this issue (Figure 1).6–9 Fur-
thermore, such soluble precursors are versatile because they allow
the generation of sophisticated morphologies.10 For p-type organic
semiconductors, a wide range of soluble precursors has been devel-
oped.6–15 In contrast, comparable soluble precursors for n-type sem-
iconductors remain elusive and would thus represent highly attrac-
tive research targets.16–21 In addition, the development of new design
guidelines for soluble precursors should be important as current
strategies rely mainly on three approaches: retro-Diels–Alder reac-
tions, decarbonylative aromatizations, and thermal removal of pe-
ripherally attached tert-butoxycarbonyl groups.
Figure 1. Soluble precursors for organic semiconductors.
Perylene bisimide (PBI) is a promising prospective n-type organic
semiconductor.22–32 However, the current design guidelines for solu-
Several organosulfur compounds are susceptible to sulfur-extru-
sion reactions (Figure 2).33–45 For example, thiepine undergoes 6π-
ble precursors are not suitable for PBI owing to the following two
electrocyclization even at –70 °C to afford thianorcaradiene, which
provides benzene from subsequent intermolecular collisions
(eq.1).41–44 Wolf and co-workers have reported that photo-irradia-
tion of 9-to-9' sulfoxide-bridged anthracene dimer results in a rapid
loss of the bridging SO unit to afford 9,9'-bianthracene (eq. 2).45
Consequently, organosulfur compounds could potentially serve as
soluble precursors for π-systems via sulfur-extrusion. Besides, our
group has reported that the conceptual insertion of a nitrogen atom
represents an effective strategy to create nonplanar and soluble PBI
analogues.46 Herein, we report the synthesis and properties of
dinaphtho[1,8-bc:1',8'-ef]thiepine bisimide (DNTBI) and its oxides
reasons: i) PBI does not contain a suitable six-membered ring for
retro-Diels–Alder reactions or decarbonylative aromatizations; ii)
thermal removal of tert-butoxycarbonyl groups from imide-nitro-
gens affords only hydrogen-substituted PBIs, despite the im-
portance of imide-substituents to control the solid-state molecular
arrangement, electron mobility, and device stability. Therefore, the
development of a different strategy is essential for the design of ver-
satile PBI precursors.
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as soluble precursors for PBI (eq.3). Notably, these precursors un-
derwent photo-induced and thermal sulfur extrusion reactions al-
most quantitatively, enabling the fabrication of a high-performance
solution-processed n-type organic field-effect transistor. Such dual
stimuli-responsibility has been limited to norbornadienone deriva-
tives among soluble precursors for organic semiconductors.6–9
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Figure 3. X-ray crystal structure of 2b. (a) Top and (b) side views. Ther-
mal ellipsoids at 50% probability. All hydrogen atoms and propyl groups
omitted for clarity.
Figure 2. Sulfur-extrusion reactions.
The synthesis of DNTBIs as well as the corresponding sulfoxides
and sulfones is shown in Scheme 1. The nucleophilic aromatic sub-
stitution of brominated naphthalene monoimide dimers46 1a (R =
C8H17) and 1b (R = C4H9) with sodium sulfide afforded DNTBIs 2a
and 2b in 47% and 48% yield, respectively. The molecular structure
of 2b was unambiguously determined by a single-crystal X-ray dif-
fraction analysis (Figure 3). DNTBI 2b shows a bent structure, in
which the sulfur atom protrudes from the π-surface. Such a distorted
conformation resembles that of a previously reported nitrogen-in-
serted PBI analogue.46 Subsequently, 2a and 2b were oxidized with
m-chloroperbenzoic acid (mCPBA, 1.0 equiv) to afford the corre-
sponding sulfoxides 3a and 3b in 78% and 84% yield, respectively.
Moreover, the tungsten-catalyzed oxidation47 of 2a and 2b with hy-
drogen peroxide provided sulfones 4a and 4b in 95% and 85% yield,
respectively.
DNTBI 2a, sulfoxide 3a, and sulfone 4a are soluble in common
organic solvents such as CH2Cl2, toluene, EtOAc, THF, and DMF.
The solubility values (S g/100 g CH2Cl2) of 2a (2.9), 3a (0.51), and
4a (5.4) are 150–1700 times higher than that of the parent PBI 5a
(3.3 × 10–3) (Figure S19). The substantially high solubility of 2a, 3a,
and 4a is most likely due to their nonplanar structures.48,49
Figure 4. UV/vis absorption spectra of 2a, 3a, 4a, and 5a (solid lines)
and fluorescence spectrum of 4a (green dashed line) in CH2Cl2. λ: wave-
length, ε: extinction coefficient.
Scheme 1. Syntheses of DNTBIs and their oxides
The UV/vis absorption spectra of 2a, 3a, 4a, and PBI 5a as well as
the emission spectrum of 4a are shown in Figure 4. The absorption
spectra of 2a, 3a, and 4a are hypsochromically shifted relative to that
of 5a, which can be attributed to the disrupted conjugation around
the inserted sulfur atom. DNTBI 2a exhibited an absorption maxi-
mum at 397 nm together with a weak absorption between 420 and
500 nm, whose spectral features resemble that of the aforemen-
tioned nitrogen-inserted PBI analogue.46 Sulfoxide 3a and sulfone 4a
displayed absorption maxima at 433 and 434 nm, respectively, which
are substantially red-shifted relative to that of 2a. Sulfone 4a exhib-
ited green emission at 510 nm with a moderate fluorescence
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quantum yield (FF = 52%). The emission spectra of 2a and 3a were
not recorded due to the formation of PBI 5a upon photoexcitation
(vide infra).
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Scheme 2. Reduction of DNTBI 2a and sulfoxide 3a
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We examined the sulfur-extrusion reactions by electron-injection.
Treatment of 2a and 3a with decamethylcobaltocene (CoCp*2) fol-
lowed by quenching with chloranil afforded PBI 5a in 59% and 89%
yield, respectively (Scheme 2). The generation of PBI 5a was also
triggered by electrochemical reduction as proven by cyclic voltam-
metry (Figure S20) and spectroelectrochemical measurements
(Figure S26–29). The results of density functional theory (DFT)
calculations suggested that the radical anion of 2a exhibits a short-
ened C–C distance (2.716 Å) between the two α-carbons of the cen-
tral sulfur atom compared to that of the neutral form (2.871 Å) (Fig-
ure S24). Furthermore, an isomerization pathway from the radical
anion to a thianorcaradiene-like species seems feasible (Figure S25).
This intermediate would most likely engage in intermolecular colli-
sions to provide the radical anion of PBI, which is similar to a path-
way that has been proposed for the extrusion of sulfur from thiepine
(Figure 2, eq. 1).41–44
We monitored the changes in the absorption spectra of DNTBI
2a and sulfoxide 3a upon photo-irradiation (Figure 5). The experi-
ments were conducted under an N2 atmosphere and the solvent
(CH2Cl2) was degassed by N2 sparging. The photo-irradiation was
performed by a high-pressure mercury lamp equipped with a sharp
cut filter (λ> 380 nm). Interestingly, the characteristic absorption of
PBI 5a gradually appeared between 450 and 550 nm, accompanied
by clear isosbestic points. The absorption spectra after photo-irradi-
ation for 1200 s are almost identical to that of 5a, indicating a nearly
quantitative conversion. The reaction of 3a is faster than that of 2a.
The photo-induced generation of PBI 5a from 2a and 3a was also
confirmed by a 1H NMR analysis (Figures S30,31). In contrast, sul-
fone 4a shows no distinct change upon irradiation (Figure S32). The
photo-induced sulfur-extrusion reactions of 2a and 3a can be re-
tarded by sparging with air (Figure S33a). A similar result was ob-
served for 9-to-9' sulfone-bridged anthracene dimer.45 These results
may suggest the possible involvement of a triplet state species as an
intermediate. It is also worth noting that the reaction rate is virtually
independent on the solvent polarity, implying that the formation of
charge-transfer states does not play an important role (Figure S33b).
Figure 5. Changes in the UV/vis absorption spectra of 2a and 3a upon
photo-irradiation in CH2Cl2 under an N2 atmosphere. For the photo-ir-
radiation, a high-pressure mercury lamp equipped with a sharp cut filter
(λ> 380 nm) was employed. [2a]0 = [3a]0 = [5a] = 4.2 × 10–5 M–1.
Figure 6. (a) TGA profiles of 2a, 3a, and 4a; heating gradient: 5.0 °C
min–1. (b) Solid samples of (i) 2a and (ii) 3a before and after heating.
To examine the effect of heating on the sulfur-extrusion reactions,
thermogravimetric analyses (TGA) were conducted on 2a, 3a, and
4a (Figure 6). The TGA profiles of DNTBI 2a and sulfoxide 3a ex-
hibited mass decreases of 4% and 6% at 300 and 225 °C, respectively,
which agrees well with the expected changes for the formation of PBI.
In contrast, the TGA profile of sulfone 4a showed a weight loss of ca.
70% around 400 °C, indicating thermal decomposition. The 1H
NMR and thin-layer chromatography analyses of the brown samples
formed upon heating 2a and 3a indicate an almost quantitative for-
mation of PBI (Figure S35,36). It is worth noting that heating crys-
talline solids of 2a for 1 h at 300 °C provided a waxy PBI solid (Figure
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6b and S34a). Considering that the melting point of PBI 5a is higher
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exhibited a distinct peak due to d-spacing of 21.6 Å (Figure S40),
which is comparable to that of the vacuum-deposited film (d-spacing
= 20.3 Å) and the XRD pattern predicted from the crystal structure
of 5a (d-spacing = 19.6 Å). The difference of surface morphologies
before and after thermal conversion was examined by atomic force
microscopy (AFM). While the surface before heating was very
smooth, relatively rough surface with several grains was observed af-
ter heating probably due to the release of gas during sulfur-extrusion
reaction and/or the crystallization of PBI (Figure 7c). The root
mean square (RMS) roughness value was calculated to be 16.1 nm.
Further examinations, especially the effect of photo-conversion and
development of a reliable procedure with high reproductivity, are ac-
tively underway in our groups.
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than 350 °C, this change of solid morphology by heating indicates
that the sulfur-extrusion reaction of 2a proceeds after melting. Con-
versely, the solid sample of 3a remained crystalline even after heating
to 250 °C for 1 h (Figure S34b). Its powder X-ray diffraction pattern
was identical to that of PBI 5a (Figure S37). In addition, the progress
of thermal conversion for the spin-coated film of 3a on a glass sub-
strate at 230 °C was monitored by measuring the UV/vis absorption
spectra, which indicates that the sulfur-extrusion reaction was com-
pleted within 2 min and the further annealing caused no apparent
degradation (Figure S38). We also examined the cooperative effect
of light and heat for the conversion of crystalline samples of sulfoxide
3a to PBI 5a (Figure S44). At 140 °C, photoirradiation slightly in-
creased the amount of PBI. These preliminary results are promising
for the creation of flexible devices with PEN or PET substrates.
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In summary, we have synthesized dinaphtho[1,8-bc:1',8'-
ef]thiepine bisimides (DNTBIs) 2a,b as well as the corresponding
sulfoxides 3a,b and sulfones 4a,b. The molecular design is based on
the insertion of a sulfur atom into a perylene bisimide (PBI) core. A
single-crystal X-ray diffraction analysis confirmed that DNTBI 2b
adopts a nonplanar structure owing to the embedded seven-mem-
bered ring. The distorted conformation endows these sulfur-con-
taining PBI analogues with excellent solubility. Notably, DNTBI 2a
and sulfoxide 3a undergo sulfur-extrusion reactions upon electron-
injection, light-irradiation, or heating. In particular, the light- and
heat-induced sulfur-extrusion reactions proceed almost quantita-
tively. These features enable the fabrication of a high-performance
organic FET with the electron mobility of up to 0.41 cm2 V–1 s–1.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Pub-
lications website.
Experimental details and spectral data for all new compounds.
Crystallographic data (CIF files) for 3b.
AUTHOR INFORMATION
Corresponding Author
hyamada@ms.naist.jp, fukui@chembio.nagoya-u.ac.jp, hshino@chem-
bio.nagoya-u.ac.jp
Figure 7. Morphologies and FET properties of a spin-cast film of 3a
after heating. (a) Optical micrograph. (b) Polarization optical mi-
crograph. (c) AFM image. (d) Transfer characteristics. (e) Output
characteristics.
Funding Sources
The authors declare the absence of any potentially competing financial
interests.
Bottom-gate top-contact field-effect transistor (FET) devices
were fabricated (Figures 7 and S39–43). The substrate surface was
ACKNOWLEDGMENT
modified with
a self-assembled monolayer of 12-cyclohex-
This work was supported by JSPS KAKENHI grant JP17H01190
and JP20K15257. H.S. thanks the Sumitomo Foundation for finan-
cial support. N.F. gratefully acknowledges the Tatematsu Founda-
tion and Iketani Science and Technology Foundation for financial
support. We thank Prof. Masami Kamigaito and Dr. Mineto
Uchiyama (Nagoya University) for thermogravimetric analyses. We
thank Prof. Yukihatu Uraoka, Dr. Mutsunori Uenuma, Dr. Takuya
Okabe (NAIST), and Prof. Mitsuharu Suzuki (Osaka University)
for the frequency-dependent capacitance measurements of dielec-
tric layer.
yldodecylphosphonic acid (CDPA) on an Al2O3/SiO2 dielectric
layer.50 A CHCl3 solution of sulfoxide 3a (5 g L–1) was spin-coated
on the substrate (30 s; 2000 rpm). The substrate was heated at
230 °C for 5 min under a nitrogen atmosphere to cause the extrusion
of sulfur. Gold electrodes were vacuum-deposited on the active layer
as source and drain electrodes. Subsequently, OFET properties were
measured at ambient temperature under vacuum conditions (>
2×10–1 Pa). The obtained OFETs exhibited typical n-type behavior.
The average and maximum electron mobilities μe are 0.13 and 0.41
cm2 V–1 s–1, respectively, with a threshold voltage Vth of 23 V and an
on/off current ratio Ion/Ioff of 3×105. The small hysteresis is observed
in the transfer characteristic (Figure S41). These mobilities are com-
parable to that of the vacuum-deposited film of 5a (μe = 0.6 cm2 V–1
s–1).51 A polarized optical microscopy analysis indicated that this
spin-coated film is polycrystalline. The XRD pattern of this film
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