Article

pubs.acs.org/Langmuir

Study of Compression-Induced Supramolecular Nanostructures of an

Imidazole Derivative by Langmuir−Blodgett Technique
Bapi Dey,† Pintu Debnath,† Santanu Chakraborty,‡ Barnali Deb,§ Debajyoti Bhattacharjee,†
Swapan Majumdar,§ and Syed Arshad Hussain*,†
†
Thin Film and Nanoscience Laboratory, Department of Physics, and §Department of Chemistry, Tripura University,
Suryamaninagar, Agartala 799022, West Tripura, Tripura, India
‡
Department of Physics, NIT Agartala, Jiraniya, Agartala 799046, West Tripura, Tripura, India
*
S Supporting Information

ABSTRACT: In this communication, we report the design and synthesis as

well as the supramolecular assembly behavior of a 2,4,5-triaryl imidazole
derivative (compound 1) at the air−water interface and in thin films using
Langmuir−Blodgett (LB) technique. The main idea for such a chemical
structure is that the long alkyl chain and N−H of the imidazole core may help
to form supramolecular architecture through the hydrophobic−hydrophobic
interaction and hydrogen bonding, respectively. Accordingly, the interfacial
behavior as well as morphology of 1 in thin films were studied through a
series of characterization methods such as surface pressure−area (π−A)
isotherm, hysteresis analysis, ultraviolet−visible (UV−vis) absorption and
steady-state fluorescence spectroscopies, Fourier transform infrared, X-ray
diffraction, Brewster angle microscopy (BAM), and atomic force microscopy
(AFM) measurements, and so forth. Pressure−area isotherm is an indication
toward the formation of supramolecular nanostructures instead of an ideal
monolayer at the air−water interface. This has been confirmed by the hysteresis analysis and BAM measurement at the air−water
interface. AFM images of 1 in the LB monolayer exhibits the formation of supramolecular nanowires as well as nanorods. By
controlling different film-forming parameters, it becomes possible to manipulate these nanostructures. With the passage of time,
the nanowires come close to each other and become straight. Similarly, nanorods come close to each other and form bundles of
several rods in the LB films. H-bonding, J-aggregation, as well as compression during film formation might play a key role in the
formation of such nanostructures. Electrical switching behavior of compound 1 was also observed because of the presence of an
electron donor−acceptor system in 1. This type of organic switching behavior may be promising for next-generation organic
electronics.

■ INTRODUCTION
Electronic and optoelectronic devices1−7 impact many areas of
switching devices, and so forth. Over the last few decades,
tremendous progress has been made in the development and
modern society from simple household appliances to investigation of such new organic materials15−19 with a readily
communications and sophisticated medical instruments. polarizable structure for the fabrication of novel devices. A
Given the demand for ever more compact and powerful conjugated π-system end-capped with a strong electron donor
systems, there is growing interest in the development of group, such as −NR2 and OR, and a strong electron acceptor
nanoscale devices that can enable new functions and/or have group, such as −NO2, cyano (CN), or imine (CNR), in a
greatly enhanced performance. Recent extensive studies have molecule generates a dipolar push−pull system (D−π−A) that
shown that organic nanomaterials exhibit a variety of interesting assures intramolecular charge transfer and low energy barrier
optical, electrical, photoelectric, and magnetic properties in the and shows an intense charge-transfer band. The extent of
solid state. Accordingly, photo- and electroactive organic electronic or optoelectronic behavior depends primarily on
materials have been the subject of current research,8−10 their chemical structure, high chemical and thermal robustness,
including organic semiconductors, organic metals, organic good solubility in common organic solvents, and availability in
superconductors, organic photoconductors, organic photoactive reasonable quantities. Hence, various five- and six-membered
materials for solar cells, organic nonlinear optical materials, heterocycles are utilized as suitable π-conjugated chromophore
liquid crystals, and others. In addition, organic materials have backbones because they act as auxiliary donors or acceptors and
found a number of potential applications for use in electronic
and optoelectronic devices,11−14 such as sensors, plastic Received: May 24, 2017
batteries, solar cells, field-effect transistors (FETs), optical Revised: July 27, 2017
data storage, organic electroluminescent devices (OLEDs), Published: August 9, 2017

© 2017 American Chemical Society 8383 DOI: 10.1021/acs.langmuir.7b01750

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improve the overall polarizability of the chromophore.20−23 In structures using conventional amphiphiles in LB films.44
this respect, five-membered diazoles, in particular imidazole, Specially designed molecules with a suitable architecture and
seems to be suitable for parent π-conjugated backbones. functional group can only form such interesting complex
Imidazole possesses two nitrogen atoms of different electronic nanostructures onto thin films using the LB technique.45 There
nature, represents a robust and stable heterocycle, and can are few reports of nanotubes and nanorods of organic
easily be synthesized and further functionalized at positions of molecules at the air−water interface and in LB films because
the imidazole core.24−26 In view of the above-mentioned of the compression-induced rolling of a nanosheet.45−47 Both
structural features and having in mind the utility of thin films in chiral as well as achiral molecules were found to form such
making devices, we have designed and synthesized 2,4,5-triaryl nanostructures. A series of rod−coil molecules consisting of the
imidazole derivative 1 having a long alkoxy chain in the 4- imidazole moiety were found to form nanowire/nanorod-like
position of the aryl group located at C-2 of the imidazole core structures because of chirality and formation of J-aggregates in
(Figure 1).27 The idea is that the oxygen atom in position 4 can LB films.48 Various kinds of nanostructures of a series of
different Schiff base amphiphiles due to supramolecular
assembly using the LB technique have also been reported.49−53
It was also observed that the imidazole derivative became chiral
in LB films when coordinated with a silver ion and formed
supramolecular nanostructures.54 In that respect, it would be
interesting to study the supramolecular assembly of 1 at the
air−water interface and in thin films using the LB technique.
In this manuscript, we report the design of an important
imidazole derivative 1 and the investigation of its supra-
molecular organization at the air−water interface and in thin
films using the LB technique. Compression-induced nanorod-
and nanowire-like structures were formed in the LB film.
Hydrogen bonding and aggregation at the air−water interface
and in the solid substrate played a key role in forming such a
Figure 1. Chemical structure of 2,4,5-triaryl imidazole derivative (1) nanostructure. The interfacial behavior as well as morphology
and 1-benzyl-2,4,5-triaryl imidazole derivative (2). in the thin film were studied through a series of characterization
methods such as surface pressure−area (π−A) isotherm,
act as an electron donor and the CN group in the imidazole hysteresis analysis, ultraviolet−visible (UV−vis) absorption
core or other phenyl aryls at C-4 or 5 can act as an electron and steady-state fluorescence spectroscopies, Fourier transform
acceptor, and therefore it is expected that some sort of infrared (FTIR), X-ray diffraction (XRD), Brewster angle
polarization may occur within the molecule in a particular microscopy (BAM), and atomic force microscopy (AFM)
environment. The long alkyl chain and N−H of the imidazole measurements, and so forth. These studies are important to
core will help to form supramolecular architecture through the have an idea about the formation mechanism as well as the
hydrophobic−hydrophobic interaction and intermolecular condition of formation of such supramolecular nanostructures
association through hydrogen bonding, respectively. using the LB technique. Although supramolecular nanostruc-
Nanofabrication using the Langmuir−Blodgett (LB) techni- tures in a thin film using organic molecules are very important
que provides a useful platform to construct supramolecular for many potential applications because of their unique
functional materials at the air−water interface and onto thin properties, very few works have been reported till now.
films.28−32 Here, the monolayer or multilayer of supramolecular
assemblies can be formed via the bottom-up assembly.33−35
Using the LB technique, not only the molecular orientation but
■ EXPERIMENTAL SECTION
Materials. Benzil, ammonium acetate, and 4-hydroxybenzaldehyde
also the molecular arrangement as well as the nature of were purchased from Spectrochem Pvt. Ltd. 1-Bromooctadecane,
molecular aggregation can be tuned to a certain extent in a two- benzyl bromide, and HBF4 were purchased from Across Organics.
dimensional manner.36,37 It is the LB technique, which triggers Ammonium acetate, ethyl acetate, dimethylformamide (DMF), and
us to dream about molecular electronics where the organic anhydrous K2CO3 were purchased from Fisher Scientific, India.
molecules will perform an active function in the processing and Working solutions were prepared by dissolving them in spectroscopic
transmission of information as well as storage. grade chloroform (SRL, India). These materials were used as received.
Since its inception, LB technique has been used for the Synthesis of 2-(4-O-Octadecyloxyphenyl)-4,5-diphenyl Imi-
dazole (1). A mixture of benzil (2 mmol), 4-O-octadecyloxy
fabrication of uniform mono/multilayer thin films using benzaldehyde (2 mmol), ammonium acetate (5 mmol), and HBF4−
amphiphilic molecules.36 However, recent studies have revealed SiO2 (0.08 g, contains 2 mol % of HBF4) was heated until the
that the LB technique can also be used to prepare other disappearance of starting materials [thin-layer chromatography
sophisticated morphologies, such as vesicles or nanotubes, (TLC)]. After completion of the reaction, the solid product along
nanorods, nanostripes, nanofibers, and their arrays.37,38 These with the catalyst was filtered. The catalyst was recovered by dissolving
complex structures in LB films are very important because of the product in ethyl acetate and washing with the same. The
their unique photophysical and photochemical properties. concentration of the solution containing the product was followed by
Application of nanostructures prepared by supramolecular recrystallization from ethanol to afford the corresponding substituted
imidazole product, 2-(4-O-octadecyloxyphenyl)-4,5-diphenyl imida-
interfacial assembly toward photodynamic therapy/antitumor zole (1). Yield 81%; colorless solid, mp 98−100 °C; IR (KBr) νmax:
therapy has already been demonstrated.39−42 Layer-by-layer 3448, 2916, 2845, 1597, 1588, 1495, 1465, 1394, 1250 cm−1; 1H NMR
self-assembled diamond-based core−shell nanocomposites have (300 MHz, CDCl3): δ 782 (d, J = 7.5 Hz, 2H), 7.49 (br s, 4H), 7.28
been found as highly efficient dye absorbents for wastewater (m, 6H), 7.04 (br s, 1H), 6.87 (d, J = 7.8 Hz, 2H), 3.92 (br s, 2H),
treatment.43 It is hardly possible to form such complex 1.76 (t, J = 6.6 Hz, 2H), 1.27 (br s, 30H), 0.89 (t, J = 6.6 Hz, 3H); 13C

8384 DOI: 10.1021/acs.langmuir.7b01750

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Figure 2. Surface pressure (π) vs area per molecule (A) isotherm of 1. The inset shows the hysteresis of 1. 1 moiety considered as a cuboid box; (i−
iii) three possible orientations of 1 at the air−water interface.

NMR (75 MHz, CDCl3): δ 159.9, 146,2, 132.5, 129.8, 128.5, 127.9, (PerkinElmer, LS 55), respectively. The attenuated total reflection
127.4, 127.0, 121.9, 114.8, 68.1, 31.9, 29.7, 29.6, 29.4, 29.3, 29.2, 26.0, (ATR)-FTIR spectra of the LB films deposited onto a ZnSe single-
22.7, 14.1; HRMS requires for C39H53N2O (M + H+) 564.4157; found, crystal were recorded using an FTIR spectrophotometer (PerkinElmer,
565.4159. model no. Spectrum 100, USA). BAM images were taken by using a
Synthesis of 1-Benzyl-2-(4-O-octadecyloxyphenyl)-4,5-di- commercial BAM system (Accurion nanofilm ep4-bam, serial no.
phenyl Imidazole (2). To a stirred mixture of 2-(4-O-octadecylox- 1601EP4030) equipped with a 30 mW laser emitting p-polarized light
yphenyl)-4,5-diphenyl imidazole (1, 1 mmol), anhydrous K2CO3 (2 at 532 nm wavelength, which was reflected off the air−water interface
mmol) in dry DMF (5 mL) and benzyl bromide (1.25 mmol) were at the Brewster angle (53.1°). XRD (Bruker D8 advance) data were
added at 60 °C and was continued until the disappearance of the obtained using monochromatic copper Kα radiation (wavelength 1.54
starting materials (∼4 h). After completion of the reaction (TLC), the Å) and 2θ step of 0.02°. The current−voltage (I−V) characteristics
mixture was filtered and washed with ethyl acetate (25 mL). The were measured using a Keithley 2401 source meter.
combined organic layer was extracted with water (25 mL), washed Procedures. To measure the isotherms and for film preparation,
with water (3 × 20 mL), dried over Na2SO4, and concentrated under 120 microliters of chloroform solution (0.5 mg/mL) of 1 was spread
reduced pressure. The crude product was purified by column with a microsyringe onto the subphase of pure Milli-Q water (18.2
chromatography using 2−5% ethyl acetate−hexane to afford the MΩ cm) at room temperature. After complete evaporation of the
desired product. Yield 89%, white powder, mp 90 °C; IR (KBr) νmax: volatile solvent, the barrier was compressed at a rate of 5 mm/min to
3020, 2941, 2856, 1597, 1467, 1369, 1270 cm−1; 1H NMR (300 MHz, record the surface pressure−area per molecule isotherm. The surface
CDCl3): δ 7.71 (m, 1H), 7.55 (m, 4H), 7.34−7.13 (m, 10H), 6.90 (d, pressure (π) versus average area available for one molecule (A) was
J = 9.0 Hz, 2H), 6.80 (m, 2H), 5.08 (s, 2H), 3.96 (t, J = 6.6 Hz, 2H), measured by a Wilhelmy plate arrangement.36 Smooth fluorescence
1.80−1.67 (m, 4H), 1.48−1.40 (m, 2H), 1.25 (s, 26H), 0.88 (t, J = 6.6 grade quartz plates (for spectroscopy) and Si-wafers (for AFM studies)
Hz, 3H); 13C NMR (75 MHz, CDCl3): δ 159.7, 137.6, 131.1, 130.9, were used as the solid substrate. This was followed by the Y-type
130.4, 129.7, 128.8, 128.7, 128.5, 128.0, 127.3, 126.8, 126.3, 126.0, deposition at a particular surface pressure to transfer Langmuir films at
114.6, 68.1, 48.2, 31.9, 30.55, 29.7, 29.6, 29.5, 29.4, 29.3, 29.2, 26.0, a deposition speed of 5 mm/min. For AFM measurements, both
22.7, 19.2, 14.1; HRMS requires for C46H59N2O (M + H+) 564.4627; single-layer and multilayer films were deposited. The transfer ratio was
found, 655.4627. estimated by calculating the ratio of decrease in the subphase area to
Instruments. A commercially available LB film deposition the actual area on the substrate coated by the layer and was found to
instrument (Apex 2000C, Apex Instruments Co., India) was used be 0.98 ± 0.02. For the I−V characteristic study, freshly cleaned
for surface pressure−area isotherm measurements as well as for indium tin oxide (ITO)-coated glass plates were used as the solid
monolayer and multilayer film preparation. The AFM images of the substrate, and 60-layer LB films of 1 were deposited onto ITO-coated
monolayer films were taken by a commercial Innova AFM system glass substrates at 10 mN/m surface pressure. Here, the ITO-coated
(Bruker AXS Pte Ltd.) by using silicon cantilevers with a sharp, high glass substrate serves as the anode and a gold tip, softly touching the
apex ratio tip (Veeco Instruments). The AFM images presented here surface of the thin film, acts as the cathode, giving an active area of 1
were obtained in the intermittent-contact (“tapping”) mode. UV−vis mm2 for measurement. The solutions were churned up for almost 10 h
absorption and fluorescence spectra of pure solutions as well as LB before the preparation of the films, and the as-prepared LB films were
films were recorded by using an absorption spectrophotometer dried for more than 10 h before characterization. During the
(PerkinElmer, Lambda 25) and a fluorescence spectrophotometer experiment, the samples were not allowed to be irradiated by any

8385 DOI: 10.1021/acs.langmuir.7b01750

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Figure 3. (A) Optical image; AFM images of the one-layer LB film of 1 at 5 mN/m (B) on optically blank space, (C) zoomed image, (D) analysis
spectra of a single nanowire, (E) on optically shown structures, (F) zoomed image, and (G) analysis spectra of a single nanorod.

light and were always kept at room temperature. The I−V curves were shows the resulting isotherm of two successive compression and
recorded by applying a sweeping voltage between 0 and 3 V at a decompression experiments. The result showed completely irreversible
voltage scan rate of 2.5 mV/s. behavior with a marked shift toward the lower area per molecular

■ EXPERIMENTAL RESULTS
Surface Pressure−Molecular Area Isotherm. To study the
region. This result supports the fact that molecule 1 did not form a
stable monolayer at the air−water interface rather formed stacking of
multilayers or high-level supramolecular structures.57 It has been
assumed that the origin of hysteresis observed in the compression−
monolayer forming behavior of 1, surface pressure−area (π−A)
isotherms of 1 at the air−water interface were recorded using the LB expansion experiment for the Langmuir film is associated with the
technique. Figure 2 shows the π−A isotherm of 1 at the air−water manifestation of strong intermolecular interactions via π−π
interface. The isotherm was repeated several times and almost interactions between the benzene ring and/or hydrogen bonding
reproducible results were obtained. The curve presented here is the between the N−H group, resulting in the formation of aggregates/
average of three independent measurements. The isotherm shows the stacks at the air−water interface.57,58
onset of surface pressure at a molecular area of 0.43 nm2/molecule To have the visual information, the floating film at the air−water
(lift-off area) with the gaseous phase extending up to 0.32 mN/m interface was investigated using BAM. The BAM images were taken at
(corresponding area per molecule = 0.37 nm2). Then, the surface various stages during the pressure−area isotherm measurement. All
pressure rises smoothly up to 35.5 mN/m. No clear phase change images clearly show that a uniform monolayer did not form at the air−
between the liquid and condensed states is observed. Also, any sharp water interface rather definite rodlike structures were formed at the
collapse at the end of the π−A isotherm is not visible, indicating the air−water interface, although the size and packing change at different
formation of domains/multilayer instead of an ideal monolayer.47 To stages of the isotherm. Representative images are shown in Figure S1
have more insight into the system, an understanding about the of the Supporting Information.
possible molecular orientation of 1 at the air−water interface is An investigation of the floating behavior of molecule 1 at the air−
necessary. On the basis of molecular modeling (CPK model) water interface suggested that molecule 1 did not form a true
considering the 1 moiety as the cuboid box (Figure 2), the dimensions monolayer at the air−water interface rather formed a multilayer or
are estimated as 1.739 nm × 0.8 nm × 0.34 nm. These dimensions aggregates. To confirm whether there was free space available at the
lead to three cross-sectional areas 1.391, 0.591, and 0.272 nm2 (Figure air−water interface just after spreading, we measured the π−A
2i−iii). Our observed value of limiting molecular area was 0.25 nm2, isotherms by varying the concentration as well as the amount of the
obtained from the extrapolation of the linear part of the isotherm to spread solution (Supporting Information, Figure S2). This also helped
zero surface pressure. Though the value of the limiting molecular area to start the isotherm with higher initial area per molecule. However,
is very close to 0.272 nm2, for the vertical orientation (Figure 2ii), such interestingly all isotherms were found to be almost similar except in
a conformation is almost unlikely because of the absence of any polar certain cases where because of low concentration, surface pressure did
group on the molecular backbone at the bottom for this orientation. not increase much. These results confirmed that the observed
The other two possible orientations of the molecule at the air−water multilayer or aggregates of molecule 1 at the air−water interface was
interface are also not possible because of the large difference in their not due to very high concentration of the spread solution. Rather, the
cross-sectional areas from the observed limiting molecular area of 1. observed stacking/multilayer formation at the air−water interface was
These facts do not support the formation of a monolayer at the air− due to different kinds of interactions among the molecules at the air−
water interface. Such results may occur either from the stacking of water interface. Our later investigations revealed the nature of such
multilayers or from the formation of high-level supramolecular interactions.
structures.55,56 This may be due to the strong interaction between Morphology of the Transferred Films. Pressure−area isotherm
molecules in the assembly. The interaction includes the hydrogen of 1 was an indication that 1 did not form an ideal monolayer at the
bonding between the N−H groups, hydrophobic interaction between air−water interface rather indicated toward the formation of
the alkyl chains, and π−π interaction between the 1 molecules. supramolecular nanostructures. To get an insight into the morphology
To have more information about the floating film at the air−water of the possible nanostructures formed at the air−water interface, the
interface, successive compression−expansion cycles were also floating Langmuir monolayer of 1 was transferred onto a solid
performed during the isotherm measurement. The inset of Figure 2 substrate under various conditions for further characterization.

8386 DOI: 10.1021/acs.langmuir.7b01750

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Table 1. Width of Nanowires and Nanorods at Different Pressures in the One-Layer LB Film of 1
width of nanostructures at pressure
structures 5 mN/m 10 mN/m 15 mN/m 20 mN/m
nanowires 110 nm 200 nm 140−150 nm 75−100 nm
nanorods 200−250 nm 500 nm 700 nm 250−300 nm

Initially for AFM characterization, the monolayer of 1 was deposited

onto a clean smooth silicon substrate at 5 mN/m surface pressure
following a vertical (Y-type) deposition mode. Before measuring the
AFM image, the film was observed through an optical microscope.
Interestingly, optical microscope images (Figure 3A) suggest two
different morphologies: (i) few parts with accumulated structures and
(ii) parts with optically blank areas. During AFM imaging, specific
attention was given to study these two different regions.
The AFM images measured on the optically blank region exhibit
wirelike nano-structures throughout the film (Figure 3B). The lengths
of the nanowires were several micrometers long. The diameter and
height of the individual nanowires were approximately 100−110 and
6−8 nm, respectively (Figure 3C,D).
On the other hand, the AFM images measured on the area of the 1
LB film, showing structures (optically visible), revealed assemblies of
nanorod-like structures having a length of 8−10 μm (Figure 3E). The
width and height of the rods were approximately 200−250 and 20−22
nm, respectively (Figure 3F,G). The AFM images of the nanowires
and nanorods with different scan areas for the same 1 in the LB film
are shown in Figures S3 and S4, respectively, in the Supporting
Information.
Pressure Effect. To check the effect of surface pressure on the
morphology of nanostructured LB films of 1, the floating films was
transferred onto a silicon wafer substrate at different surface pressures
viz. 10, 15, and 20 mN/m. Under an optical microscope, all films Figure 4. (A) AFM images of nanowires in the one-layer LB film of
showed regions with two different morphologies: blank surface as well the 1 molecule at 10 mN/m. (B) Analysis spectra of nanowires. (C)
as accumulated regions as seen in the film deposited at 5 mN/m Nanorods in the one-layer LB film of 1 at 15 mN/m. (D) Analysis
surface pressure. The AFM images of all films showed either nanowire- spectra of nanorods.
or nanorod-like structures for two different regions in the films.
However, variation in the size and shape/organization of nanostruc-
tures in the films was observed depending on the surface pressure of
the deposition (Table 1).
In the case of the nanowire, although the height remained almost
the same, the width changes with the surface pressure, and maximum
width was observed for the film deposited at 10 mN/m (Figure 4A,B
and Table 1). On the other hand, in the case of the nanorod, both the
width as well as height changed with the surface pressure. Initially,
both the width and height increased with surface pressure and then
decreased. Maximum height and width were observed for the film
deposited at 15 mN/m surface pressure (Figure 4C,D and Table 1).
Several other AFM images for different pressures in one-layer 1 LB
film are shown in the Supporting Information (Figure S5).
Aging Effect. Supramolecular organic nanostructures play a key
role toward organic electronics through improvement of semi-
conducting, conducting, memory, storage, and display performances.
It has been observed that 1 formed organized nanowire- and nanorod-
like structures in LB films. An understanding of the time-dependent
changes in such nanostructures is very important for their application.
Accordingly, the morphology of 1 LB films with passage of time was
studied using AFM. To do that, one-layer LB film of 1 was deposited
on a smooth clean silicon substrate, and the morphology of the film
surface was studied using AFM at regular intervals for several days.
Our observation revealed interesting results. Although the width
and thickness of the individual nanowire and nanorod remained almost
unaltered with the passage of time, the alignment and organization of Figure 5. (A) AFM images of the nanowire after 5 days in the one-
the nanorod and nanowire changed in the LB films with the passage of layer LB film of the 1 molecule at 5 mN/m. (B) Analysis spectra of the
time. Initially, the organization of the nanowires in the LB films was nanowire. (C) Nanorods after 5 days. (D) Analysis spectra of the
arbitrary with hardly any definite directionality. However, with passage nanorod.
of time, the nanowires came close to each other and became straight
with respect to each other in the LB films (Figure 5A,B). As a whole,
the organization of the nanowire changed in the LB films. Such preparation of the films. However, after 5 days, almost no further
changes in the organization occurred up to 5 days from the day of changes in the film surface morphology were observed, indicating

8387 DOI: 10.1021/acs.langmuir.7b01750

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Figure 6. AFM image of the 10-layer LB film of 1 at 5 mN/m.

Figure 7. AFM image of 2 in the one-layer LB film at 5 mN/m with different scan areas(A) 20 × 20 μm2, (B) 10 × 10 μm2, and (C) 5 × 5 μm2.

attainment of maximum stable configuration of 1 nanowire in the LB

films.
■ DISCUSSION
Generally, the amphiphilic molecules can exhibit relatively
On the other hand, in the case of nanorods, with passage of time,
strong hydrophobicity as they have a quite long alkyl chain and
the nanorods came close to each other and formed bundles of several their head groups contain aromatic rings. When these
rods in the LB films (Figure 5C,D). Here also, the change in the film amphiphilic molecules are spread onto the air−water interface,
morphology occurred up to 5 days of film formation, and maximum some of them tend to assemble into multilayer films or more
stable configuration of 1 nanorod occurred within 5 days of complicated nanostructures instead of forming an ideal
preparation of LB films. Several other AFM images showing the effect monolayer.45 It has already been explained that such
of aging day by day in the nanorods and nanowires are shown in nanostructures at the air−water interface may be due to
Figures S6 and S7, respectively, in the Supporting Information. various noncovalent bonds such as the hydrogen bond, π−π
Layer Effect. Compound 1 formed supramolecular structures in stacking of the π-conjugated end groups, electrostatic
the one-layer LB film. To check the effect of multilayer deposition of interaction, hydrophobic interaction of the hydrophobic spacer,
the nanostructures of 1 onto LB films, 10-layer LB films of floating 1 and so forth.59
films were deposited onto a silicon substrate and studied using AFM. In the present case, the absence of a sharp collapse and the
Corresponding AFM images (Figure 6A) showed interesting results observed lower value of the limiting area per molecule in the
with modified nanostructures. surface pressure versus area per molecule isotherm of 1
Here, the nanowires (formed in one-layer LB films) are broken in suggested that imidazole derivative 1 did not form an ideal
length, and several broken nanowires are bundled together to form monolayer at the air−water interface. It has been reported that
nanorod-like structures (Figure 6D). The width is 4−5 times and the 2-(heptadecyl)naphtha[2,3]imidazole (NplmC17) also did not
height is almost double (Figure 6E) compared to the nanowires that form an ideal monolayer and showed a too small limiting area
formed in one-layer LB films (Figure 3D). However, the length was per molecule.54 The observed small molecular area suggested
within the 1−2 μm range. the strong interaction between the 1 molecules within the
On the other hand, in the case of multilayer films, the nanorods are assemblies, which may include the hydrogen bonding of the
attached with each other. Here, four to five nanorods join together to N−H group, hydrophobic interaction between the alkyl chain,
form bigger bundles in the multilayer LB films (Figure 6B,C). and also π−π interaction. These features of the isotherm are an
8388 DOI: 10.1021/acs.langmuir.7b01750
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indication of the formation of supramolecular nanostructures of

1 at the air−water interface.60 Liu et al. observed a small area
per molecule when cinnamoyl-terminated bolaamphiphiles
formed aggregated nanostructures at the air−water inter-
face.45,59 Azobenzene derivative also formed surface pressure-
driven supramolecular structures showing a small molecular
area at the air−water interface.47
The AFM image of 1 LB film showed the formation of
nanowires and nanorods in a one-layer LB film. We assume that
the intermolecular H-bond between N−H of one imidazole
ring and N of another neighboring 1 molecule may play a
crucial role in the formation of such nanostructures in the LB
films. To check this possibility, we synthesized a new molecule
(compound 2) having an almost similar structure to that of 1.
The only difference is that the N−H group present in 1 was
replaced by a benzyl group in 2. After that, we prepared a one-
layer LB film of 2 onto a silicon wafer and investigated using
AFM. The AFM analysis revealed that the 2 molecule did not
Figure 8. FTIR spectra of 1 in the KBr pellet (black) and in the 10-
form nanostructures in LB films. AFM images for 2 in the LB layer LB film (red) along with the FTIR spectra of 2 in the LB film
monolayer are shown in Figure 7. The interesting thing is that (green) deposited at 5 mN/m. The inset shows the magnified FTIR
because of the absence of the N−H group in the molecular spectra of 1 in the wavelength range of 1200−1700 cm−1 for better
structure of 2, no H-bonding formed at the air−water interface. comparison.
Accordingly, no nanostructures were observed. This justified
our assumption that the H-bonding between the N−H and  has been observed that compound 2 did not form any
N groups of the neighboring 1 molecule in case of 1 assembly supramolecular nanostructures like molecule 1 in LB films. It
at the air−water interface and in the LB film plays a vital role in has been assumed that because of the absence of N−H group,
the formation of supramolecular nanostructures in one-layer LB no H-bond formed in case of compound 2 in LB films.
films. Liu et al. also reported that imidazole derivatives formed Accordingly, no nanostructures were observed. To justify this
different kinds of nanostructures because of H-bonding hypothesis, FTIR spectra of 2 were also measured and are
between the N−H group present in the molecular structure presented in Figure 8. The absence of a band system within
and J-aggregate formation in the LB films.48 There are several 3100−4000 cm−1 clearly confirmed that no H-bonding was
reports where it has been explained that because of H-bonding, formed in the LB film of molecule 2.
different nanostructures were observed in the LB films under It has been reported that π−π stacking in J-aggregates as well
various conditions.44,45,59,61 as other aggregates, for example H-aggregate, plays an
FTIR spectroscopy is a powerful tool to have an idea about important role toward the formation of different kinds of
vibrational changes during the molecular interaction. This supramolecular structures in LB films.46,48 To check the
method is particularly very useful for investigating the system possible aggregation nature of 1 in the LB film, we have
where a reaction has occurred. We also measured the FTIR recorded the UV−vis absorption and fluorescence spectra of 1
spectra of molecule 1 in the LB film as well as in the KBr pellet. in solution and in LB films. The solution spectrum of 1
Important band positions are listed in Table 2, and the possessed a prominent intense 0−0 band at 303 nm. For LB
corresponding spectra are shown in Figure 8. films of 1, an overall broadened absorption spectrum appeared
at 321 nm along with a red shift of 18 nm with respect to pure
Table 2. Important Band Positions in the FTIR Spectra of 1 1 in solution. The broadening of the absorption spectrum along
in the KBr pellet and in LB Films with the red shift may be due to the formation of J-aggregates
in LB films. The corresponding absorption spectra of 1 in
band positions (cm−1)
(compound 1) solution and in the LB film are given in the Supporting
Information (Figure S8). The fluorescence spectrum of 1 in
in KBr pellet in LB film band assignment band shift (cm−1)
solution showed a prominent peak at 396 nm, whereas in the
3448 3415 N−H stretching vibration 33 case of the LB film, the same has been shifted to 387 nm.
2919 2915 CH2 asymmetric vibration 4 Excitation spectra with monitoring wavelength fixed at the
2849 2840 CH2 symmetric vibration 9 emission maximum for both the solution and LB film have also
1465 1477 CH2 scissoring vibration 12 been recorded. The observed difference in the excitation
1250 1241 CH2 wagging vibration 9 spectra for the solution and film with respect to the band
position and broadening also confirmed the possible
Indication about the H-bonding has been confirmed from the aggregation of molecule 1 in LB films. The corresponding
observed difference in the position as well as intensity of the fluorescence spectra and excitation spectra are shown in Figure
N−H stretching vibration between the FTIR spectra in the LB S9 of the Supporting Information. Therefore in the present
film and in the KBr pellet. Nitrogen in the imidazole molecule case, in addition to H-bonding, J-aggregate also played a crucial
can form H-bonds with hydrogen in the N−H group of the role toward the formation of nanostructures in LB films.
neighboring molecule.48 On the other hand, the bands due to On the basis of the experimental results of AFM and
the vibration of CH2 of the alkyl chain are largely affected in the spectroscopic investigations, we tried to propose a model
LB film compared to that in KBr. This clearly indicated the (Scheme 1) for the formation of nanowires and nanorods at the
change in orientation of the alkyl chain in LB films.45,49−51,59 It air−water interface and in LB films of 1. There exist few reports
8389 DOI: 10.1021/acs.langmuir.7b01750
Langmuir 2017, 33, 8383−8394
Langmuir Article

Scheme 1. Formation Mechanism of Surface Pressure-Driven Supramolecular Nanostructures

showing the formation of such nanowire- and nanorod-like nanosheet-like structure at the air−water interface after
assembly of organic amphiphiles.45−48,59 They also proposed spreading because of H-bonding and J-aggregate formation.
models for the formation of such a nanoassembly.45−47 In few Upon compression, this nanosheet rolled up to form a
cases, surface pressure-driven rolling of the organized layer at nanowire/nanorod-like structure. However, in the present
the air−water interface has been suggested.45−47 In the present case, two types of nanostructures/nanowires and nanorods
case, microscopic results revealed the formation of nanowire- were formed. This may be due to a different order of stacking
and nanorod-like structures. Also, H-bonding between the N− during aggregation at the air−water interface and also the
H groups of 1 occurred at the air−water interface. On the other extent of rolling during compression.
hand, the absorption spectroscopic study suggested the We have also checked the AFM images of the drop-cast as
possibility of J-aggregate formation. In J-aggregates, molecules well as spin-coated films prepared using the same solution
are stacked together with head-to-tail arrangements.62,63 (Figure S12). Interestingly, no such nanostructures were
To have an idea about molecular organization in the observed in the corresponding images as seen in the LB
aggregates, we performed the XRD study for a 10-layer LB films. This also indicates that the LB technique has a specific
film of 1. The corresponding spectra is shown in the role in the formation of observed supramolecular nanostruc-
Supporting Information (Figure S10). The XRD spectra show tures (nanowire/nanorod) in thin films.
prominent sharp peaks with 2θ = 22.03, 38.28, 44.43, 64.91, It has been observed that the width and height of the
68.86, and 79.18°, indicating the formation of an ordered nanostructures changed with an increase in the surface pressure
crystalline structure in the LB films. A similar feature in the of lifting. This may be due to a change in the extent of stacking
XRD spectra for other imidazole derivatives has also been of the 1 molecule in the aggregate before the rolling occurred
reported.64,65 The calculated layer distance was found to be on with surface pressure during compression. On the other hand,
the order of 0.4 nm corresponding to 2θ = 22.03° using Bragg’s with aging, organization of 1 nanowires changed. They seemed
equation. This distance is assigned to the distance between two to be straightened with aging and became stable after few days.
adjacent 1 molecules in the longitudinal direction.66 Consid- Also, several nanorods came close to each other and formed
ering the dimensions of the present molecule as 1.739 nm × 0.8 bundles with aging. There might exist some interaction
nm × 0.34 nm, the observed distance is consistent with the between the corresponding nanostructures within the film,
typical distance for effective π−π stacking between the aromatic resulting in modification of the alignment as well as
molecules. This suggests that molecule 1 remained flat arrangement in the films. Absorption spectroscopic study
horizontally in the multilayer. (Figure S8) of the 1 LB film with aging also showed some
Therefore, it might be possible that because of H-bonding, changes of the aggregation band, indicating a change in the
aggregation nature in the LB films with time. However, after
several 1 molecules might connect together horizontally at the
few days, the film attained stable condition. It is relevant to
air−water interface and stack together to form a large
mention in this context that a change in the aggregation nature
nanosheet-like arrangement at the air−water interface. Also,
in the LB film has already been reported by several authors.67,68
there exists a strong hydrophobic interaction due to the
It has been explained as due to the molecular movement that
presence of a long alkyl chain of the 1 molecule.59 Owing to the
occurred within the LB film resulting in a change in
strong hydrophobicity upon compression, the nanosheet/layer aggregation.69,70
may tend to roll up into a nanowire or nanorod.46 To check the
effect of compression on the formation of 1 nanostructure, we
deposited a film of 1 onto a Si-substrate at zero surface
pressure. The AFM image of the corresponding film did not
■ SWITCHING BEHAVIOR
Organic nanostructures assembled onto LB films are very
show any nanowire/nanorod-like structures (Figure S11) as promising with respect to their possible application in
seen in the film deposited at definite pressures. Therefore, it molecular electronic devices.71 In the present study, imidazole
can be said that in the present case, the 1 molecule formed a derivative 1 formed nanostructures when organized onto LB
8390 DOI: 10.1021/acs.langmuir.7b01750
Langmuir 2017, 33, 8383−8394
Langmuir Article

films. Imidazole derivatives can readily form a donor−acceptor (TCNQ) showed resistive switching behaviur.82 Using Raman
system when tailored with various aromatic groups and possess spectroscopy, it has been confirmed that anions were changed
various attractive properties in terms of conductivity, into neutral components during the charge transfer process.83
luminescence, and color tunability.72−74 We do believe that Chu et al. also reported bistable switching phenomenon using
nanostructures of 1 in LB films may be an interesting input [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and
toward the component of future organic electronic devices. tetrathiofulvalene (TTF) because of charge transfer in the
Here, we have investigated the electrical switching behavior donor−acceptor moiety.80 It has also been observed that the
of 1 assembled onto LB films. In a switching device, two threshold voltage changed with the aging of 1 in LB films. In
conducting states (low and high) are observed at the same the present case, the observed switching behavior was due to
applied voltage.75 This type of bistable organic switching the charge transfer between the donor−acceptor sites of
behavior is promising for next-generation information storage compound 1. However, further investigations are required to
and future optoelectronic devices.76,77 We expected the know the exact mechanism of switching behavior of compound
switching behavior using 1 because of the presence of the 1 in LB films. Also, we do believe that an identical study of
electron donor−acceptor group in the 1 molecule (Figure 1). optical and electrical behaviors of compound 1 in thin films
A typical I−V characteristic curve of 1 in the LB film is may give some valuable information toward its practical
shown in Figure 9. As a reference, the I−V characteristic of application in optoelectronic devices. Investigations are going
on in this line in our lab.

■ CONCLUSIONS
In summary, we have designed a 2,4,5-triaryl imidazole
derivative and studied its assembly behavior at the air−water
interface and in thin films by the LB technique. This molecule
may be an interesting candidate for organic electronics because
of the presence of oxygen atom in position 4, which can act as
the electron donor, and the N group or other phenyl aryls at
C-4 or 5, which can act as the electron acceptor in 1, to
generate a dipolar push−pull system (D−π−A) that assures
intramolecular charge transfer. Also, the long alkyl chain and
N−H of the imidazole core may help to form supramolecular
architecture through the hydrophobic−hydrophobic interaction
and hydrogen bonding. The absence of a sharp collapse and the
observed lower value of limiting area per molecule in the
pressure−area isotherm of 1 indicated the formation of
domains/multilayer instead of an ideal monolayer. This was
confirmed by hysteresis analysis and BAM measurement. AFM
Figure 9. I−V characteristic of 1 in the 60-layer LB, spin-coated, and investigations successfully demonstrated the formation of
drop-cast films. The inset shows the I−V characteristic of blank ITO.
supramolecular nanowire- as well as nanorod-like structures
in LB films. The height and width of the individual nanowires
blank ITO has also been presented in Figure 9 (inset) for were nearly 6−8 and 100−110 nm, respectively. For nanorods,
comparison. From the figure, it can be observed that pure ITO the height and width were nearly 20−25 and 200−250 nm,
showed linear Ohmic behavior as expected.9,78,79 On the other respectively. We have found that the morphology of such
hand, clear switching behavior can be observed for molecule 1 nanostructures were strongly dependent on the surface pressure
in the LB film. During scanning at lower voltage, the film of deposition and layer number as well as on aging. The height
exhibited its low conducting state (OFF state) initially. When of the nanowires remained almost same but the width changed
the voltage approached the so-called threshold voltage (about with surface pressure, and maximum width was observed at a
1.5 V), the current increased rapidly, showing its high surface pressure of 10 mN/m. In case of nanorods, both the
conducting state (ON state). width as well as height changed with surface pressure, and
To check the role of the LB technique on such observed maximum value (width 700 nm and height 70 nm) was
switching behavior, we also prepared drop-cast as well as spin- observed for the film deposited at 15 mN/m surface pressure.
coated films of 1 on the ITO-coated glass substrate and Upon aging, the morphology of such nanostructures changed in
checked their I−V characteristics. However, the observed LB films. With passage of time, the nanowires came closer to
results (Figure 9) did not show any switching phenomenon, each other and became straight with respect to each other in
rather showed linear Ohmic behavior. This clearly indicates the the LB films. The nanorods also came closer to each other with
role of the LB technique toward the electrical switching the passage of time and formed bundles of several rods in the
behavior of molecule 1. LB films. Such changes occurred within 5 days of film
Because of the presence of the electron donor−acceptor formation, and no further changes occurred afterward. In case
system in the 1 molecule, electrical charges are particularly of 10-layer LB films, the nanowires were broken in length, and
transferred from the donor to the acceptor moiety in LB several broken nanowires were bundled together to form a
films.80,81 However, in the case of drop-cast/spin-coated films, nanorod-like structure. On the other hand, four to five
the charge transfer may be disturbed because of the bulk nature nanorods joined together to form bigger bundles in the
of the films. A sharp increase in conductivity occurred after the multilayer LB films. FTIR spectra clearly indicated the
charge had been transferred. Because of the presence of the formation of H-bonding and change in the orientation of the
donor−acceptor group, Cu−tetracyanoquinodimethane alkyl chain in the LB film of 1. UV−vis and fluorescence spectra
8391 DOI: 10.1021/acs.langmuir.7b01750
Langmuir 2017, 33, 8383−8394
Langmuir Article

revealed the formation of J-aggregate of 1 in LB films. The

formation of an ordered crystalline structure in the LB films has
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8394 DOI: 10.1021/acs.langmuir.7b01750

Langmuir 2017, 33, 8383−8394