A Novel Bat-Shaped Dicyanomethylene-4H-pyran-Functionalized Naphthalimide for Highly Efficient Solution-Processed Multilevel Memory Devices

Article abstract of DOI:10.1002/asia.201700438

Small-molecule-based multilevel memory devices have attracted increasing attention because of their advantages, such as super-high storage density, fast reading speed, light weight, low energy consumption, and shock resistance. However, the fabrication of small-molecule-based devices always requires expensive vacuum-deposition techniques or high temperatures for spin-coating. Herein, through rational tailoring of a previous molecule, DPCNCANA (4,4′-(6,6′-bis(2-octyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)-9H,9′H-[3,3′-bicarbazole]-9,9′-diyl)dibenzonitrile), a novel bat-shaped A-D-A-type (A-D-A=acceptor–donor–acceptor) symmetric framework has been successfully synthesized and can be dissolved in common solvents at room temperature. Additionally, it has a low-energy bandgap and dense intramolecular stacking in the film state. The solution-processed memory devices exhibited high-performance nonvolatile multilevel data-storage properties with low switching threshold voltages of about ?1.3 and ?2.7 V, which is beneficial for low power consumption. Our result should prompt the study of highly efficient solution-processed multilevel memory devices in the field of organic electronics.

Full text of DOI:10.1002/asia.201700438

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: A Novel Bat-Shaped Dicyanomethylene-4H-pyran-Functionalized
Naphthalimidefor Highly Efficient Solution-Processed Multilevel
Memory Devices
Authors: Jian-Mei Lu, Qi-jian Zhang, Shi-feng Miao, Hua Li, Jing-hui
He, Na-jun Li, Qing-feng Xu, and Dong-yun Chen
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10.1002/asia.201700438
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A Novel Bat-Shaped Dicyanomethylene-4H-pyran-Functionalized
Naphthalimidefor Highly Efficient Solution-Processed Multilevel
Memory Devices
Qi-jian Zhang, Shi-feng Miao, Hua Li, Jing-hui He, Na-jun Li, Qing-feng Xu, Dong-yun Chen & Jian-mei
Lu*
Abstract: Small molecule based multilevel memory device has
attracted increasing attentions since the advantages as super-high
storage density, fast reading speed, light weight, low energy
consumption, and shock resistance. However, the fabrication of
small molecule-based device always needs expensive vacuum
deposition techniques or high temperature for spin-coating. In this
paper, through rationally tailoring of the previous molecule
DPCNCANA, a novel bat-shaped A-D-A-type symmetric framework
has been successfully synthesized, and can be dissolved in common
solvents under room temperature. Meantime, it processes low
bandgap in energy and densely intramolecular stacking in film state.
The solution-processed memory devices exhibited high-performance
nonvolatile multilevel data storage properties with low switching
threshold voltages of about 1.3 V and 2.7 V, respectively, which is
beneficial for low-power consumption. Our result will prompt the
study of highly efficient solution-processed multilevel memory
devices in the field of organic electronics.
environment. Thus, reasonably design novel small molecules
which can dissolve in common solvents under room temperature
remains a big challenge for future UHDDS utilities.
In our previous work, we successfully fabricated a small
molecule DPCNCANA based memory device with improved
ternary data-storage performance through cyano substitution in
the backbone.6 However, it still has some little drawbacks, such
as relatively large threshold voltage, room-meat-square
roughness and bandgap between HOMO and LUMO energy
levels. Additionally, according to the XRD measurement,
DPCNCANA was lack of densely intramolecular stacking in film
state, resulting in the charge carriers have difficulty in
transporting through the neighbor molecules. Therefore,
rationally tailoring of this chemical structure may overcome
these problems and form a novel small molecule with excellent
solution-processing properties.
Herein, we report a novel A-D-A-type bat-shaped small
molecule: 2-(2,6-bis((E)-2-(9-(2-ethylhexyl)-6-(2-octyl-1,3-dioxo-
2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)-9H-carbazol-3-
yl)vinyl)-4H-pyran-4-ylidene)malononitrile, s-DCMCzNI (Figure
1a). The design of A-D-A configuration s-DCMCzNI,
Introduction
Organic multilevel memory devices (OMMDs),1,2 representing
one of the most promising and low-cost technology for future
ultra-high density data storages (UHDDS), can exponentially
increase the data storage capacity of the device to 3n in
comparison to binary memory systems,3,4 under external
electrical or optical stimulus.1a,2a–c However, they generally
require complex physical evaporation or expensive vacuum
deposition techniques in device production process. To enable
low-cost and large-scale manufacturing, devices fabrication
through simple solution process under ambient conditions is
highly desirable.5 Till now, o-DCB was widely used for the
fabrication of small-molecule based OMMDs under high
temperature or with ultrasonic, which was mainly due to the
reason that the D-A structured molecules we synthesized were
with large conjugated backbones thus were extremely hard to
dissolve in common solvents.2,6 Nevertheless, o-DCB can cause
seriously sporadic irritation of the eyes and respiratory tract,
incorporates
the
electron-accepting
octyl-substituted
naphthalimide (NI) as end-capping unit not only to extend the π-
conjugated structure, but also to provide solution processing and
change the solid-state molecular ordering.7,8 The extented π-
conjugation and planarity of the molecule is expected to
enhance intermolecular π–π interactions and thereby promote a
highly-ordered molecular packing, which could facilitate charge
carrier transport.2b,4b,9 The end-capping NI acceptor is linked
through carbazole (Cz) unit, which is a large conjugated
electron-rich arylamine system, resulting in strong intramolecular
charge transfer.10 Incorporation of 2-ethylhexyl aliphatic
branched chain on the nitrogen position of Cz is to ensure good
solubility of the molecule in organic solvents.9c In this work, we
also introduce the 4-(dicyanomethylene)-4H-pyran (DCM) unit
as the electron-deficient core because of its high electron
affinity,11 making it a good electron acceptor.
s-DCMCzNI exhibits excellent solubility in common
organic solvents, 1 mg s-DCMCzNI can dissolve rapidly in 0.1
mL CH2Cl2, CHCl3, ClCH2CH2Cl, THF or DMSO, as shown in
Figure S1. Additionally, s-DCMCzNI based film shows a
smooth root-mean-square surface with densely intramolecular
stacking. Moreover, s-DCMCzNI based memory device shows
excellent ternary data storage performance with a relatively low
Qr. Q. Zhang, Dr. S. Miao, Prof. H. Li, Prof. J. He, Prof. N. Li, Prof. Q. Xu,
Dr. D. Chen,Prof. J. Lu
College of Chemistry, Chemical Engineering and Materials Science,
Collaborative Innovation Center of Suzhou Nano Science and Technology,
Soochow University, Suzhou 215123, P. R. China. Fax: +86 512
65880367; Tel: +86 512 65880368;
E-mail: lujm@suda.edu.cn
switching threshold voltages of –1.33 V and –2.75 V,
respectively, which is beneficial for low power consumption.This
work further manifests that the NI and DCM moieties can serve
as the charge traps with different depth to block the movement
Supporting information for this article is given via a link at the end of the
document.
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of the charge carriers thus to realize the ternary memory
behaviours. Furthermore, we also open a new way to control the
whole molecular electrical properties and the corresponding
memory device performance through the tailoring of “bat’s brain”
in the molecular backbone.
reported literatures. Aldol condensation of 1 and 2 under the
basic condition readily afforded 3 in 64% yield. Compound 5 was
prepared by Suzuki coupling reaction of
4
with
bispinacolatodiborane with Pd(dppf)Cl2 as the catalyst in dry
toluene. s-DCMCzNI was obtained also via Suzuki cross-
coupling reaction of 3 and 5. It is worthy to note that commonly-
used solvent toluene only afforded trace product regardless of
increasing reaction time and temperature because of poor
solubility of starting materials in toluene. When employing a
small amount of THF as the co-solvent, the reaction proceeded
smoothly with a moderate yield of 46%. The detailed synthesis
of these three molecules is depicted in the Experimental Section.
Results and Discussion
Molecular structures and synthesis routes
The synthesis of s-DCMCzNI is outlined in Scheme 1.
Compounds 1,12 2,13 414 were synthesized according to the
Scheme 1.Chemical structures and synthesis routes of the molecule s-DCMCzNI.
The Fabrication of Memory Devices with ITO glasses and
PET substrates
Figure 1b shows the fabrication of the sandwich-structured
memory device on ITO glasses. The indium-tin-oxide (ITO)
glasses were sequentially pre-cleaned with water, acetone, and
alcohol in an ultrasonic bath for 20 min, successively. The s-
DCMCzNI solution was dissolved in 1,2-dichloroethane (10
mg/mL) and filtered through microfilters with a pinhole size of
0.22 µm, after then the solution was spin-coated on the
substrates and the solvent was removed in a vacuum chamber
at 10–3 Torr and 60 °C for 16 hrs, and the film thickness was
measured to be about 80 nm. An aluminum (Al) layer with
thickness of about 130 nm and diameter of about 0.5 mm was
thermally evaporated and deposited onto the organic layer
surface at about 5 × 10–6 Torr through a shadow mask to form
the top electrode. An active device area of about 0.0314 mm2
was obtained.
Subsquently, memory devices with conductive PET substrate
were also fabricated, and the fabrication procudure is similar to
the devices with ITO glass substrate. The flexible devices can
be bent into different bending degrees, which can be defined by
the distance between the end of the arc (D) or the radius of the
curvature (R), as shown in Fig. S6.
Figure 1. (a) The bat-shaped small molecule s-DCMCzNI. (b) SEM image
(left) of a cross-section view of the sandwich device (right) based on s-
DCMCzNI.
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Photophysical and Electrochemical Properties
of s-DCMCzNI was 0.71 eV, which was lower than that between
Φ of Al electrode (-4.28 eV) and the LUMO energy levels (1.02
eV). This indicated that hole injection from ITO electrode into the
molecular HOMO level was easier than the electron injection
from top Al electrode into the molecular LUMO level (Table S1).
Therefore, s-DCMCzNI was an p-type semiconductor material,
and the memory behaviors were dominated by hole-
transporting.6 Additionally, the relatively low level of the LUMO
for s-DCMCzNI was conductive to prevent electron from trapping
by O2 and could realize good air stability and high electron
transport, which was mainly resulted from the chemical inertness
of NI moieties, the electron-deficient sp2 N atoms in cyano units
and finally the large conjugated system.16 All these
characteristics are beneficial for the outstanding performance of
s-DCMCzNI based memory device.
Electric Properties
The
indium-tin
oxide
(ITO)/s-DCMCzNI/Al
sandwich-
configuration devices fabricated from simple spin-coating
process with ITO as substrate and Al as top electrode. The
current–voltage (I–V) characteristics of such devices are shown
in Figure 3. As can be seen in Figure 3a, the s-DCMCzNI-based
memory devices initially showed a low-conductance state (OFF
or “0” state) under no bias voltage. When a negative voltage was
applied to the Al electrode and increased further, an abrupt
increase in current occurred at about –1.33 V, indicating the
transition of the devices from OFF state to intermediate-
conductance state (ON1 or “1” state). As the voltage
approached –2.75 V, a second sharp increase in current
occurred, which indicated that the device switched from an ON1
state to a high-conductance state (ON2 or “2” state) (sweep 1).
This OFF-to-ON1 or ON1-to-ON2 transitions is equivalent to
“write” process in a digital memory cell. The second sweep was
to measure another cell of the device over a voltage range of 0
to –2.0 V, and the OFF to ON1 state transition was also
observed when approaching a voltage of –1.30 V. After the
transition, the devices remain in the ON1 state during the
subsequent sweep from 0 to –2.0 V even after turning off the
bias voltage or applying reverse bias (sweep 3 and 4). In
addition, the cell could be programmed from the ON1 state to
the ON2 state when the bias voltage was increased to –4.0 V
(sweep 5), and the high-conductance state could also be
maintained during the subsequent scan from 0 to –4.0 V even
after removing the power supply or applying positive bias
voltage (sweep 6 and 7). This device, therefore, demonstrates
typical non-volatile ternary WORM memory behaviour. From the
measurements, we found that the threshold voltages were
indeed lower than our previous DPCNCANA based memory
device, which was inconsistent with the lower bandgap
calculated from the UV spectrum.
Additionally, the three states could be clearly distinguished from
each other by an ON/OFF current ratio of 1 : 102.1 : 104.3 when
read at –1 V. It should be worthy of note that our devices are
highly stable after proper data writing and that a constant
voltage (e.g., –1.0 V) can be used to read the “0”, “1” and “2”
signals of the memory devices (Figure 3b). There is no
significant degradation in any of the three states for almost ten
hours. Furthermore, the effect of continuous read pulses of –1 V
on the OFF, ON1 and ON2 states was also investigated. The
pulse period and interval are 2 μs and 1 μs, respectively, as
shown in the inset of Figure 5c. No obvious degradation in the
current was observed for all three states after up to 108
continuous read cycles, suggesting that none of the three states
was sensitive to read pulses.
Figure 2. (a) UV-vis absorption spectra of s-DCMCzNI in dilute THF solution
(blue) and as a thin film spin-coated from 1,2-dichloroethane on quartz
substrate (red). (b) Cyclic voltammogram of s-DCMCzNI in dichloromethane
containing n-Bu4PF6 electrode at a scan rate of 100 mV/s.
Thermogravimetric analysis (TGA) data indicate the
decomposition temperature (5% weight loss) to be 274 °C
(Figure S2), reflecting good thermal stability for s-DCMCzNI. UV-
vis absorption spectra of s-DCMCzNI in dilute THF solution and
as-cast thin film are shown in Figure 2a. In dilute solution, s-
DCMCzNI has a strong absorption peak at 452 nm, which could
be assigned to the intramolecular charge transfer (ICT) between
the electron-donors and the electron-acceptors.15 Compared
with the absorption features in solution, the spun-cast film from
1,2-dichloroethane reveals a visible red-shift of the maximum,
and simultaneously the onset, suggesting molecular aggregation
and coplanarity in the solid state.7 The absorption onset for the
spun-cast film is 550 nm, corresponding to an optical bandgap of
2.25 eV, which is lower than that of the previously molecule
DPCNCANA with 2.67 eV. Thus, we assume that the threshold
voltage of s-DCMCzNI based memory device should be lower
than DPCNCANA based memory devices.
Cyclic voltammetry (CV) was used to estimate the HOMO
energy (Figure 2b). The onset of oxidation at 1.27 V, vs Ag/AgCl,
yields a HOMO energy of –5.51 eV, and from the optical
bandgap and measured HOMO, the LUMO energy is estimated
to be –3.26 eV (Figure S3). The energy barriers between the
work function (Φ) of ITO (-4.80 eV) and the HOMO energy levels
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In order to confirm the feasibility of s-DCMCzNI-based memory
devices, we measured the electric properties under different
bending conditions, as shown in Figure S6. The s-DCMCzNI-
based memory device exhibited the ternary memory behaviors
even with the D bending to 20 mm, as shown in Fig. S7b.
However, the memory device showed no distinct ternary
memory behaviors with the D under 15 mm (Fig. S7c and 7d). In
addition, the memory device was stable under a constant
reading voltage of -1 V with the D bending to 20 mm for about
104 s without degradation (Fig. S8).
Figure 3. Current–voltage (I–V) characteristics (a), effect of the operation time (at –1 V) on the device current in the “0”, “1”, and “2” states (b), and effect of a read
pulse of –1 V on the three states of ITO/s-DCMCzNI/Al device (c).
To further understand the low switching threshold voltage of the
memory device, atomic force microscopy (AFM) was employed
to probe the surface morphology of the as-cast s-DCMCzNI films.
Topographic image of the as-cast film, shown in Figure 4 with a
scan size of 5 × 5 μm2, exhibits continuous fiber-like features,
which was similar like what has been observed on other DCM
derivatives.7 Figure 4b shows the cross-section profile of the
AFM height image, indicative of the root-mean-square (RMS)
surface roughness is less than 1 nm, which is much lower than
DPCNCANA based film, thus is favourable for lowering down the
energy barrier between the electrodes and the active layers.
Therefore, less energy is needed for the charge carriers to
overcome the energy barriers, which may also interpret the
lower threshold voltages of this memory device.17
Molecular Stacking in Film
From AFM image, we can only probe the surface morphology.
To probe the internal morphology, X-ray diffraction (XRD)
measurement was carried out. As shown in Figure S4, the as-
cast films exhibit an evident XRD peak at 2θ = 22.3°, which
corresponds to a d-spacing of 3.98 Å, implying well-ordered and
densely packed molecular structures. While DPCNCANA based
film lacked of effective densely intramolecular stacking in solid
state. Thus, the charge transfer through s-DCMCzNI based film
was more convenient than DPCNCANA based film due to the
densely molecualr stacking.
Meantime, we simulated the structural optimizations of s-
DCMCzNI, as shown in Fig. S5. The dihedral angle between the
carbazole moiety and the naphthalimide group was simulated to
be about 54.8°, which was similar to the previous molecule
Figure 4. (a) Tapping-mode AFM height image of as-cast s-DCMCzNI film on
ITO substrate and (b) typical cross-section profile of (a).
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DPCNCANA. However,to our surprise, the central DCM group
processed a nearly coplanar structure with the Cz moieties at
ground state, which might result from the introduction of the O
atom that can induce extra intermolecular H-bond in the
molecules. The coplanar structure is beneficial for the ordered
stacking in film state, which may explain the densely stacking
and the novel peak showed at 22.3°. Thus, we can conclude that
such well-arranged as-cast films are very favourable for charge
carrier injection and transport, providing a powerful guarantee
for achieving low-power consumption solution-processable
multilevel data storage devices.
Proposed memory mechanism
To better understand the switching mechanism of the memory
devices, theoretical calculation was executed to simulate the
electrostatic potential (ESP) as well as HOMO and LUMO orbital
surfaces of s-DCMCzNI. As shown in Fig. 5, an open channel
with continuous positive molecular ESP (in red) was formed
along the whole conjugated backbone, through which the charge
carriers can move freely. In contrast, the negative ESP regions
(in blue) resulting from the naphthalimide and cyanoacceptors
can serve as the “charge traps” to block the movement of the
charge carriers, and the “trap depth” is in accordance with the
electron-withdrawing capability of the electron-deficient
moieties.18 According to our previous work and the simulated
ESP result, we have determined that the electron-withdrawing
capability of cyano group was stronger than that of NI moieties.
However, in this work, we find that the charge carriers
weremoved from Cz moieties to DCM groups after the first
excitation, which is different from what we have observed in
previous molecule DPCNCANA.6
We found that the HOMO and LUMO of s-DCMCzNI are close in
energy, which are located mainly on the DCM units and part of
the Cz parts. This may be caused by the introduction of O atom
in the DCM units since C-O-C can serve as a strong electron-
donor in the backbone. Thus, the electron-accepting capability of
DCM units will be largely decreased, and the “trap depth” of
DCM based electron-acceptor will become even lower than NI.
Initially, the device is in OFF state, which is caused by the lack
of enough power to overcome the energy barrier. With the
increase of voltage, the “charge trap” arising from DCM unit will
be filled with electron quickly, causing the current switches from
OFF to ON1 state. Then NI based “charge trap” will also full of
Figure 5. Molecular electrostatic potential (ESP) surfaces and molecular
orbital energy levels of s-DCMCzNI.
Conclusions
In summary,
a novel symmetric bat-shaped A-D-A-type
naphthalimide molecule based on DCM core unit was
successfully designed and prepared. The small molecule
OMMDs by simple solution processing exhibited high-
performance non-volatile multilevel data storage properties with
a low switching threshold voltages of –1.33 V and –2.75 V,
respectively, which is beneficial for low-power consumption.
Besides, it processes a densely intramolecular stacking and
smooth surface in solid state with a relatively low bandgap in
energy, which may interpret the lower threshold voltages than
our previous mmeory device. Our result will prompt the research
on highly efficient solution-processed multilevel memory devices
in the field of organic electronics.
electron when the external electric field is swept to second Experimental Section
threshold voltage, resulting in the transition from ON1 to ON2
state. Upon undergoing the transition from HOMO to LUMO+1,
the electron density distribution will locate on NI and becomes
Materials and Instruments
more stable than initial state. Thus, the trapped electron is
All chemicals and reagents were used as received from commercial
difficult to de-trap although the power is shut down or reversed,
and then the high conductivity state can be maintained for a long
time.
sources without purification. Solvents used were dried and distilled by
standard methods prior to use.All chemical reactions were carried out
under an argon atmosphere, unless otherwise stated.NMR spectra were
obtained on anVarianInova 400 MHz or 300 MHz FT-NMR spectrometers.
High resolution mass spectra (HRMS) were obtained using MicroMass
TOF-MS spectrometer (ESI). The elemental analysis was performed by
an Italian 1106 FT analyzer. UV-vis absorption spectra were carried out
at room temperature from 300 to 650 nm with a Shimadzu UV-3600
spectrophotometer. SEM image was taken on a Hitachi S-4700 scanning
electron microscope. Atomic force microscopy (AFM) measurements
were performed by using a MFP-3DTM (Digital Instruments/Asylum
Research) AFM instrument in tapping mode. All electrical measurements
of the device were characterized under ambient conditions without any
encapsulation, using a HP 4145B semiconductor parameter analyzer
equipped with HP 8110A pulse generator.TLC analysis was performed
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on silica gel plates and column chromatography was conducted over
silicagel (mesh 200–300), both of which were obtained from the Qingdao
OceanChemicals.
80.90, H 7.08, N 6.15; found: C 80.68, H 7.17, N 6.05.HRMS (ESI): calcd
for C92H96N6O5 [M+H]+ 1365.7442, found 1365.7455.
Acknowledgements
Preparation of molecules.
This work was financially supported by the NSF of China
(21176164, 21336005), Chinese-Singapore Joint Project
(2012DFG41900) andSuzhou Science and Technology Bureau
Project (SYG201524).
2-(2,6-bis((E)-2-(6-bromo-9-(2-ethylhexyl)-9H-carbazol-3-yl)vinyl)-4H-
pyran-4-ylidene)malononitrile (3).
6-bromo-9-(2-ethylhexyl)-9H-carbazole-3-carbaldehyde (1, 1.16 g,
3
mmol), 2-(2,6-dimethyl-4H-pyran-4-ylidene)malononitrile (2, 0.26 g, 1.5
mmol), and piperidine (0.3 g, 3.5 mmol) were dissolved in dry acetonitrile
(12 mL). After refluxing for 24 hrs under argon atmosphere, the reaction
mixture was poured into water (50 mL). The resulting mixture was
extracted with dichloromethane (3 × 20 mL). The combined organic layer
was dried over anhydrous sodium sulfate and concentrated in vacuo. The
residual solid purified by column chromatography on silicagel eluted with
dichloromethane/petroleum ether (v/v, 2/1) to give 3(0.87 g, 64%) as an
orange red solid. 1H NMR (400 MHz, CDCl3) δ 8.71 (s, 2H, ArH), 8.41 (s,
2H, ArH), 8.00 – 7.91 (m, 3H, ArH), 7.71– 7.60 (m, 6H, ArH, CH=CH),
7.42 – 7.35 (m, 3H, ArH, CH=CH), 6.79 (s, 2H, CH (pyran)), 4.31 (d, J =
7.4 Hz, 4H, NCH2), 2.01 – 1.91 (m, 2H, NCH2CH), 1.38 – 1.26 (m, 16H,
CH2), 0.85 (t, J = 7.5 Hz, 6H, CH3), 0.77 (t, J = 6.9 Hz, 6H, CH3).13C NMR
(75 MHz, CDCl3) δ158.53, 155.73, 142.47, 140.15, 138.52, 129.26,
126.15, 124.42, 123.38, 122.53, 121.20, 115.76, 112.84, 111.18, 110.23,
108.11, 106.28, 58.13, 47.89, 39.61, 31.13, 28.92, 24.54, 23.22, 14.24,
11.08. Anal. calcd for C52H52Br2N4O: C 68.72, H 5.77, N 6.16; found: C
68.65, H 5.85, N 6.02.
Keywords:Small molecule • common solvents • decreased
bandgap • densely stacking • low threshold voltage
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2-octyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-
benzo[de]isoquinoline-1,3(2H)-dione (5).
3.
4.
(a) S. Moller, C. Perlov, W. Jackson, C. Taussig and S. R. Forrest,
Nature, 2003, 426, 166. (b) J. Y. Ouyang, C. W. Chu, C. R. Szmanda, L.
P. Ma and Y. Yang, Nat. Mater., 2004, 3, 918. (c) J. C. Scott and L. D.
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Zhu, D. S. H. Chan, E. T. Kang and K. G. Neoh, Prog. Polym. Sci.,
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2169.
A mixture of 6-bromo-2-octyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (4,
0.78 g, 2.0 mmol), bispinacolatodiborane (0.76 g, 3.0 mmol), (1,1’-
bis(diphenylphosphino)ferrocene)-di-chloropalladium (0.11 g, 0.2 mmol)
and potassium acetate (0.59 g, 6.0 mmol) in toluene (25 mL) was heated
to 70 oC for 16 hrs. After cooling to room temperature, insoluble
constituents were filtered off and the product was purified on silica gel
eluted with dichloromethane/petroleum ether (v/v, 1/2) to give 5 (0.54 g,
62%) as a yellowish solid.1H NMR (400 MHz, CDCl3) δ 9.11 (d, J = 8.5
Hz, 1H, ArH), 8.60 (d, J = 7.2 Hz, 1H, ArH), 8.57 (d, J = 7.2 Hz, 1H, ArH),
8.30 (d, J = 7.3 Hz, 1H, ArH), 7.78 (dd, J = 8.2, 7.5 Hz, 1H, ArH), 4.17 (t,
J = 7.7 Hz, 2H, NCH2), 1.73 (quint, J = 7.7 Hz, 2H, NCH2CH2), 1.45 (s,
(a) S. Choi, S. H. Hong, S. H. Cho, S. Park, S. M. Park, O. Kim and M.
Ree, Adv. Mater., 2008, 20, 1766. (b) J. Lee, E. Lee, S. Kim, G. S.
Bang, D. A. Shultz, R. D. Schmidt, M. D. E. Forbes and H. Lee, Angew.
Chem., Int. Ed., 2011, 50, 4414. (c) K. J. Baeg, Y. Y. Noh, J. Ghim, S. J.
Kang, H. Lee and D. Y. Kim, Adv. Mater., 2006, 18, 3179. (d) Y. Ma, X.
B. Cao, G. Li, Y. Q. Wen, Y. Yang, J. X. Wang, S. X. Du, L. M. Yang, H.
J. Gao and Y. L. Song, Adv. Funct. Mater., 2010, 20, 803.
12H,CCH3), 1.43 – 1.19 (m, 10H, CH2), 0.87 (t, J = 6.7 Hz, 3H, CH3); 13
C
NMR (100 MHz, CDCl3) δ164.33, 135.86, 135.31, 134.97, 130.90,
129.79, 127.89, 127.16, 124.82, 122.71, 84.69, 40.66, 31.98, 29.51,
29.39, 28.25, 27.33, 25.14, 22.81, 14.28. Anal. calcd for C26H34BNO4: C
71.73, H 7.87, N 3.22; found: C 71.92, H 7.67, N 3.38.
5.
6.
7.
8.
9.
B. L. Sun, M. Wen, Q. S. Wu and J. Peng, Adv. Funct. Mater., 2012, 22,
2860.
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J. M. Lu, J. Mater. Chem. C, 2015, 3, 6778.
2-(2,6-bis((E)-2-(9-(2-ethylhexyl)-6-(2-octyl-1,3-dioxo-2,3-dihydro-1H-
benzo[de]isoquinolin-6-yl)-9H-carbazol-3-yl)vinyl)-4H-pyran-4-
ylidene)malononitrile (s-DCMCzNI).
Y. L. Shang, Y. Q. Wen, S. L. Li, S. X. Du, X. B. He, L. Cai, Y. F. Li, L.
M. Yang, H. J. Gao and Y. Song, J. Am. Chem. Soc., 2007, 129, 11674.
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To adegassed (Argon) solution of 3 (175mg, 0.19 mmol) and 5 (184mg,
0.42 mmol) in toluene (5 mL), dry THF (1 mL), absolute ethanol (2 mL)
and water (5 mL) were added potassium carbonate (110 mg, 0,77 mmol)
and Pd(PPh3)4 (22 mg, 0.01 mmol). The reaction mixture was refluxed
and stirred for 24 hrs. After cooling to room temperature, the mixturewas
poured into water and extracted with dichloromethane (3 × 50 mL). The
combined organic extracts were washed with brine,dried over anhydrous
sodium sulfate, and concentrated under reduced pressure toobtain the
crude residue. The crude material was purified by column
chromatography (dichloromehane/petroleum ether, 10:1 to 30/1) to afford
title product s-DCMCzNI (121mg,46%) as a dark red solid. 1HNMR (400
MHz, CDCl3)δ8.68 (d, J = 7.5 Hz, 2H, ArH), 8.64 (d, J = 7.1 Hz, 2H, ArH),
(a) O. P. Lee, A. T. Yiu, P. M. Beaujuge, C. H. Woo, T. W. Holcombe, J.
E. Millstone, J. D. Douglas, M. S. Chen and J. M. J. Frechet, Adv.
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Miyazaki, I. Osaka and K. Takimiya, Org. Lett., 2012, 14, 4914. (c) Y. M.
Sun, G. C. Welch, W. L. Leong, C. J. Takacs, G. C. Bazan and A. J.
Heeger, Nat. Mater., 2012, 11, 44.
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Chen, Chem. Mater., 2011, 23, 4487.
11. Y. S. Yao, J. Xiao, X. S. Wang, Z. B. Deng and B. W. Zhang, Adv.
Funct. Mater., 2006, 16, 709.
8.41 (d, J = 8.3 Hz, 2H, ArH), 8.36 (s, 2H, ArH), 8.29 (s, 2H, ArH), 7.83 (d, 12. C. H. Chen, J. T. Lin and M. C. P. Yeh, Tetrahedron, 2006, 62, 8564.
J = 7.4 Hz, 2H, ArH), 7.79–7.64 (m, 8H, ArH), 7.61– 7.56 (m, 2H, ArH),
13. L. L. Woods, J. Am. Chem. Soc., 1958, 80, 1440.
7.54– 7.47 (m, 2H, CH2=CH2), 6.82 (d, J = 16.0 Hz, 2H, CH=CH), 6.66 (s,
2H, CH (pyran)), 4.29 (d, J = 6.7 Hz, 4H, NCH2CH2), 4.25 (t,J = 7.5 Hz,
14. A. L. Thompson, T. S. Ahn, K. R. J. Thomas, S. Thayumanavan, T. J.
Martinez and C. J. Bardeen, J. Am. Chem. Soc., 2005, 127, 16348.
4H, NCH2CH), 2.20 – 2.08 (m, 2H,NCH2CH), 1.81– 1.71 (m, 4H,
15. M. Hagiri, N. Ichinose, C. L. Zhao, H. Horiuchi, H. Hiratsuka and T.
NCH2CH2), 1.46– 1.29 (m, 36H, CH2), 0.99 (t, J = 7.4 Hz, 6H, CH3),
0.91– 0.88 (m, 12H, CH3).13C NMR (75 MHz, CDCl3) δ164.52, 164.33,
Nakayama, Chem. Phys. Lett., 2004, 391, 297.
158.98, 147.53, 142.85, 141.49, 138.89, 133.10, 131.28, 130.98, 130.57,
130.46, 128.99, 128.71, 128.43, 126.94, 126.57, 126.34, 123.45, 123.11,
122.20, 121.49, 120.62, 116.06, 115.83, 110.20, 109.91, 106.40, 58.20,
48.05, 40.74, 39.76, 32.04, 31.19, 29.90, 29.58, 29.46, 28.99, 28.36,
27.40, 24.61, 23.26, 22.86, 14.33, 11.16. Anal. calcd for C92H96N6O5: C
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10453.
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2014, 50, 11856.
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18. X. D. Zhuang, Y. Chen, G. Liu, B. Zhang, K. G. Neoh, E. T. Kang, C. X.
Zhu, Y. X. Li and L. J. Niu, Adv. Funct. Mater., 2010, 20, 2916.
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Table of Contents
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A
novel bat-shaped A-D-A-type
Qi-jian Zhang, Shi-feng Miao, Hua
Li*,Jing-hui He, Na-jun Li, Qing-feng Xu,
Dong-yun Chen & Jian-mei Lu*
symmetric
successfully
molecule
has
been
designed
throgh
rationally tailoring the previous
molecule DPCNCANA. The solution-
processed memory devices exhibited
densely stacking, smooth surface and
high-performance multilevel storage
properties with low switching threshold
voltages.
Page No. – Page No.
A
Novel
Bat-Shaped
Dicyanomethylene-4H-pyran-
Functionalized Naphthalimide for
Highly Efficient Solution-Processed
Multilevel Memory Devices
For internal use, please do not delete. Submitted_Manuscript
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