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Azo-linked room temperature columnar liquid crystals with bisphenol

A core: structure property relationship and photophysical properties

Hitendra Mali , Vinay S. Sharma , Anuj S. Sharma ,

Pranav S. Shrivastav , Vipin A. Rana , Hemant R. Prajapati

PII: S0022-2860(24)00028-0
DOI: https://doi.org/10.1016/j.molstruc.2024.137505
Reference: MOLSTR 137505

To appear in: Journal of Molecular Structure

Received date: 6 August 2023

Revised date: 20 December 2023
Accepted date: 4 January 2024

Please cite this article as: Hitendra Mali , Vinay S. Sharma , Anuj S. Sharma ,
Pranav S. Shrivastav , Vipin A. Rana , Hemant R. Prajapati , Azo-linked room temperature columnar
liquid crystals with bisphenol A core: structure property relationship and photophysical properties,
Journal of Molecular Structure (2024), doi: https://doi.org/10.1016/j.molstruc.2024.137505

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Highlights
 A new class of bisphenol-A linked azo mesogens has been designed and
characterized.
 All four dimeric azo mesogens showed columnar hexagonal phase.
 The structure-property relationship has been discussed for parent azo mesogens.
 These azo-ester based dimers adopted good photophysical properties.

1
Azo-linked room temperature columnar liquid crystals with bisphenol A
core: structure property relationship and photophysical properties
Hitendra Malia, Vinay S. Sharmaa*, Anuj S. Sharmaa, Pranav S. Shrivastava, Vipin A.
Ranab, Hemant R. Prajapatia,c*
a
Department of Chemistry, School of Sciences, Gujarat University, Ahmedabad, Gujarat,
India
b
Department of Physics, School of Sciences, Gujarat University, Ahmedabad, Gujarat, India
c
Department of Chemistry, Centre of Education, Indian Institute of Teacher Education,
Gandhinagar, Gujarat, India
Corresponding author: vinaysharma3836@gmail.com, drhrprajapati@yahoo.co.in

Abstract
A series of bent-shaped liquid crystals containing an azo group and a bisphenol A
core were synthesized, and characterized using various techniques. The presence of
mesogenic properties in these azo-based dimers was confirmed through POM, DSC, and
high-temperature XRD analysis. The structure-property relationship is further studied to
confirmed the effect of the variable alkyl side chain on the terminal position, which also
affects the liquid crystalline properties of the compounds in terms of mesophase temperature
range and thermal stability. All the compounds exhibited enantiotropy columnar hexagonal
phase with wide temperature range and thermal stability. Their photophysical properties were
investigated using UV-visible spectroscopy and spectrofluorometry. It was observed that all
four columnar mesogens underwent cis and trans azo isomerization upon exposure to
photoisomerization.
Keywords: Azo dye, bisphenol A, columnar phase, self-assembly, photophysical properties.

2
1. Introduction
The self-assembly process plays a crucial role in the systematic molecular design of
functional materials, leading to the creation of substances with liquid crystalline properties
[1]. These functional compounds, known as liquid crystals (LCs), have gained significant
attention for their unique combination of properties, including optics, self-assembly
capabilities, charge transport, and photochromic behavior [2-5]. Among different types of
LCs, columnar LCs have been extensively studied due to their charge transport and stacking
properties, making them highly valuable for applications in display devices [6-9]. These
compounds have demonstrated the ability to self-assemble, respond to external electric fields,
and exhibit electro-optical behavior, making them promising candidates for various scientific
fields [10,11].
Bent-shaped mesogens belong to a category of LCs that can achieve polar order
without possessing molecular chirality [12]. Various bent-core mesogens have been
documented, characterized by a wide range of central core and linker groups [13-19]. These
mesogens display properties such as columnar, smectic, and nematic phases. The
incorporation of azo (-N=N-) groups at different positions within the molecular structure's
core has led to the development of photosensitive materials with photo-tuning capabilities,
offering promising prospects for diverse applications [20-23].
Bisphenol A is a synthetic compound widely used in the production of various
materials such as epoxy resins, vinyl-ester epoxy resins, polycarbonates, and various other
types of polymers [24]. It is typically synthesized on an industrial scale by combining phenol
and acetone under acidic conditions [25]. Bisphenol A is a colourless substance that is more
soluble in organic solvents than in water [26]. It is known for its stability, having two
hydroxyl groups and a lateral methyl group, which allows for functionalization and
exploration of its liquid crystalline behavior, photophysical properties, and thermal stability.
So far, there is one published study on bisphenol A based dimers that exhibit smectic and
nematic mesomorphic behavior, featuring an ester linkage group [27]. These dimers
demonstrated mesogenic properties of the smectic and nematic types, with thermal stability
observed at temperatures of 129.0 °C and 147.7 °C, respectively (Fig. 1).

4
 Fig. 1. The proposed and reported bisphenol A based LCs [27].

In the present study, we have designed and synthesized four new liquid crystalline
compounds (E1-E4) based on azo bisphenol A. These compounds were created by
incorporating an azo-ester linker at the para-position of the central core and attaching four
alkoxy chains with varying lengths at the peripheral positions. All four derivatives displayed
a columnar phase that was stable over a wide temperature range, including at room
temperature. Furthermore, the mesogens were well characterized and their photophysical
properties (cis/trans isomers) were investigated before and after exposure to UV light. In this
report, we present the columnar liquid crystalline properties of bisphenol A based
compounds, highlighting their reversible transformation from a mesogenic to a non-
mesogenic state. Additionally, we explored the relationship between the molecular structure
and properties to gain a deeper understanding of the phase behavior, thermal stability, and the
impact of different alkoxy tail groups on this specific class of mesogens.

5
2. Materials and method
Reference standards of resorcinol, 4-amino benzoic acid, bisphenol A, ethanol, conc.
sulphuric acid, NaNO2, HCl, NaOH, K2CO3, KOH, 1-naphthol, HCl, NaNO2, N-(3-
dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC∙HCl), 4-(dimethylamino)
pyridine (DMAP) and alkyl bromides (R-Br) were purchased from Avra Synthesis Pvt. Ltd,
(Hyderabad, India). HPLC grade THF (purity of 99.9) was procured from Sigma Aldrich.
The Fourier transform infrared (FT-IR) spectra were recorded on a Bruker Tensor 27 FT-IR-
spectrophotometer in the range between 500 and 4000 cm-1. The mesophase textures were
captured and examined by a Polarizing Optical Microscope (POM) (Nikon Eclipse LV-100
POL) with temperature-controlled LTSE 420 heating stage (Linkam Scientific Instruments,
Tadworth, Surrey, UK) for temperature regulation. The 1H NMR and 13C NMR spectra were
recorded on a Bruker Advance (500 MHz) using CDCl3 solvent. The measurement of
temperature on both heating and cooling cycle was performed with the scanning rate of 10 °C
min-1 using Shimadzu Differential Scanning Calorimeter (DSC)-60 Plus. For the microscopic
study during heating and cooling cycles, the synthesized compounds were sandwiched
between a coverslip and a glass slide. The X-ray diffraction (XRD) studies were carried out
by using a glass capillary filled with target materials on a Rigaku-Ultima IV powder
diffractometer equipped with a Cu kα source (λ = 1.5418 Å) and 1.6 kW, X-ray tube with 40
kV and 30 mA as the applied voltage and current values with Philips X'PERT MPD. Further,
the target mass of the compounds was analyzed using High-Resolution Mass Spectrometer.
3. Result and Discussion
3.1 Synthesis and characterization
Scheme 1 illustrates the systematic route used to synthesize azo-ester dimers
containing bisphenol A core. To protect the acid group of p-amino benzoic acid, esterification
reaction was carried out by modifying the reported method using ethanol and H2SO4 to form
ethyl 4-amino benzoate (A) with 80% yield [28]. In the second step, the diazotization reaction
was performed using compound (A), resorcinol, NaNO2, HCl, and NaOH in an ice bath [29].
The formation of the azo dye product (B) was ascertained using starch iodide and Congo red
paper. Alkylation of compound (B) was carried out using acetone and different alkyl
bromides and K2CO3 to form di-alkoxy benzene derivatives (C1-C4) in quantitative yields
[30]. Further, the de-protection of ester was carried out using a well-known method with
NaOH and ethanol: water (7:3) to convert into acid derivatives (D1-D4) in good yields [31].
Finally, the esterification of compounds (E1-E4) was carried out by using EDC∙HCl (as a
dehydrating agent) and DMAP (as a catalyst) [32]. The reactions were initially checked by

6
TLC, and further the reaction mixture was diluted with water and extracted with
dichloromethane to obtain the target compounds (E1-E4). Purification of these materials was
performed by column chromatography using ethyl acetate: hexane (1:9) as the mobile phase.
All four dimers (E1-E4) were obtained in good yields (65–70%). The loss of yield was
primarily caused by excessive chromatographic purification to achieve high purity of the
target materials. Further, all the compounds were characterized by 1H-NMR, 13
C-NMR, IR,
UV-Vis and MALDI Tof spectral techniques.

Scheme 1: (i) H2SO4, ethanol, reflux, 3 hr; (ii) resorcinol, NaNO2, HCl, NaOH; (iii) R-Br,
K2CO3, acetone, reflux, 24 hr; (iv) NaOH, ethanol, water, 5 hr; (v) bisphenol A,
EDC∙HCl/DMAP, DCM, 24 hr, rt.

3.2 POM examination

The mesophase temperatures of the synthesized bisphenol A based azo materials (E1-
E4) were determined by POM during the heating and cooling cycles. All the bent-shaped
mesogens exhibited focal conic type texture pattern, which are commonly observed in the
columnar phase. The texture patterns observed in the mesogens were similar to those reported
in bent-shaped azo materials based liquid crystals. The mesophase pattern of compounds E1,
E2, E3, and E4 are shown in Fig. 2. The compounds with decyloxy (E1), dodecyloxy (E2),
hexadecyloxy (E3), and octadecyloxy (E4) chains exhibited liquid crystalline properties at
32.8 °C, 27.0 °C, 28.6 °C, and 30.4 °C on heating cycle, respectively. The isotropization

7
temperatures of compounds E1, E2, E3, and E4 were observed at 108.7 °C, 103.6 °C, 93.1 °C,
and 86.4 °C during the heating process, respectively. Similarly, on the cooling condition, the
isotropization temperatures were measured at 104.8 °C, 101.6 °C, 91.2 °C, and 82.7 °C for
compounds E1, E2, E3, and E4, respectively. Fig. 2 illustrates the phase behavior of these
compounds studied in relation to the transition temperature. It is evident that the mesophase
temperatures decrease as the alkyl group length increases towards the peripheral position.
Compound E3, which has an hexadecyloxy tail, displayed a wider range of mesophase
temperatures compared to the other functionalized bisphenol A-linked mesogens. The
presence of a symmetrical core composed of bisphenol A, along with functionalization
through azo and ester linkers, supported by phenyl rings, and the inclusion of bi-substituted
alkoxy tails, contributes to the manifestation of liquid crystalline properties at room
temperature. The introduction of bi-substituted longer alkoxy chains on the compound's
symmetrical core reduces crystallinity and enhances the stabilization of the mesophase at
lower temperatures. The phase sequence of compound E4 was examined at different
temperatures and further observed up to room temperature (Fig. S13). It clearly suggests the
compound E4 stabilized columnar hexagonal phase at room temperature. Similarly, rest of
three materials with their respective alkoxy side tail groups, effectively stabilized the Colh
phase at room temperature. Furthermore, all bisphenol A linked azo mesogens demonstrated
enantiotropic mesogenic behavior across a wide temperature range.

Fig. 2. POM texture images: compound E1 at 32.8 °C (a); compound E2 at 27.0 °C (b);
compound E3 at 28.6 °C (c); compound E4 at 30.4 °C (d), width of the picture is 100 µm.

8
3.3 DSC investigation
After obtaining the POM results, DSC study was conducted to confirm the formation
of the mesophase. DSC measurements were also employed to investigate the thermal
properties of the bi-substituted azo-based materials. All four compounds exhibited two
endothermic peaks during heating and cooling cylces, confirming the presence of an
enantiotropic type of liquid crystalline phase. The phase transition temperatures, along with
the corresponding enthalpies, for the azo-based materials are summarized in Table 1.
Furthermore, the temperatures obtained from the DSC analysis corresponded well with the
textural patterns observed during microscopic studies. This alignment between the DSC
results and the visual observations provides additional validation regarding the phase
behavior and thermal characteristics of the synthesized materials (Fig. S14). The introduction
of longer and more flexible alkoxy chains on the side phenyl-substituted rings led to a
decrease in the mesophase temperatures. This can be explained by the substitution of longer
alkyl chains on the bisphenol A core, which influences various molecular properties such as
dipole moment, molecular rigidity, polarity, and molecular interactions. The increased
flexibility and length of the alkyl chains disrupt the ordering of the mesophase, resulting in
lower temperatures at which the mesophase occurs [33]. A bar graph in Fig. S15 illustrates
the thermal behavior of the synthesized azo-based bisphenol A dimers. The mesogens
showed higher thermal stability confirmed by thermogravimetric analysis. The presence of
bisphenol A as the central core contributes to the improved thermal stability of the
compounds. Additionally, the presence of four ester substitutions on both sides, along with an
azo linker, enhances the stability compared to normal bent-shaped mesogens. Moreover, the
mesogens linked by azo-ester bonds exhibit a wider range of mesophase temperatures, which
can be attributed to the longer alkyl groups on the disubstituted phenyl rings. The increased
length of the alkyl chains influences the molecular packing and ordering within the
mesophase, resulting in a broader stability range.
Table 1. Phase transition temperatures [°C] of target materials, with associated enthalpies
(kJ/mol).
Compound Phase sequence
Heating ΔH (kJ/mol) Cooling ΔH (kJ/mol)
E1 Cr 37.8 (20.6) Colh 104.6 (11.6) I I 103.1 (10.7) Colh 34.6 (21.1) Cr
E2 Cr 31.7 (28.5) Colh 99.4 (10.2) I I 96.4 (12.8) Colh 30.2 (24.7) Cr
E3 Cr 29.8 (31.3) Colh 90.8 (9.8) I I 89.6 (9.7) Colh 23.5 (34.5) Cr
E4 Cr 27.4 (20.7) Colh 84.7 (12.1) I I 79.6 (8.2) Colh 28.7 (23.8) Cr

9
a
: Peak temperatures were observed on the second heating and cooling stages with a scanning
rate of 10 °C/min.
3.4 TGA examination
The thermal stability behavior of all the synthesized azo-based bisphenol A materials
was investigated using TGA, as depicted in Fig. S16. The TGA analysis provided valuable
insights into the weight loss and decomposition characteristics of the materials as a function
of temperature. All four materials (E1–E4) displayed thermal decomposition and good
thermal stability under N2 atmosphere. Initially, all four compounds show stability up to 240
°C, which suggests the ability of the compound to maintain their liquid crystalline property
under these conditions. The compounds with azo-ester groups and lower alkyl arms (E1, E2)
showed lower weight loss as compared to compounds E3, and E4 with longer alkyl arms. The
compounds (E3, E4) with hexadecyloxy and octadecyloxy side groups, exhibited slightly
higher weight loss of around 68 to 71 % at the temperature around 260 °C to 340 °C. On the
other hand, compounds E1 and E2, with decyloxy and dodecyloxy side groups, respectively,
displayed 57 to 61 % weight loss at temperatures around 270 °C to 350 °C. It can be observed
that, the length and nature of the alkyl chains can influence how well they interact with the
central functionalized mesogenic core. The presence of lower alkyl chains may lead to more
efficient packing around the core, which can enhance thermal stability as compared to the
higher alkyl chain. The decomposition of the azo mesogens is attributed to the breaking of the
azo and ester groups in the presence of the peripheral alkoxy side groups [34]. Despite this
decomposition, all four derivatives indicated their suitability for various applications that
require thermal robustness.

3.5 XRD investigation

The confirmation of the Colh phase was initially conducted through POM, while the
molecular arrangement in the mesomorphic state was investigated using XRD analysis.
Interestingly, all four materials with different alkoxy chains displayed a Colh phase, as
observed during the microscopic study. Furthermore, the arrangement of molecules in the
packing structure was studied using X-ray analysis at the transition temperatures identified
from the DSC investigation (Fig. S17). The X-ray analysis provides valuable information into
the molecular ordering and packing within the mesophase of the materials. In contrast, the
original bisphenol core does not exhibit liquid crystalline properties due to its high
nonlinearity and propensity to crystallize. However, with the introduction of an azo-ester
group and di-alkoxy substituted arms on both sides of the bisphenol core, rigidity and
flexibility are imparted to the molecular system. The structural modifications applied to the

10
bisphenol A core increased its anisometry, consequently promoting the emergence of liquid
crystalline behavior. Further, the crystallization tendency was diminished by the use of the
long alkoxy chains, which also favoured segregation and columnar phase formation. The
XRD pattern exhibited three distinct reflections in the low-angle region, indicating the
characteristic pattern of a Colh phase. Additionally, two diffused peaks were observed in the
higher-angle region. These observations suggest the presence of core-core interactions, such
as π-π stacking, and interactions resulting from the tetra-substituted alkoxy chains on both
terminal ends of the molecules. For instance, compound E1 displayed three peaks at 3.3°,
6.2°, and 7.4°, corresponding to calculated d-spacing values of 26.78 Å, 14.27 Å, and 12.96
Å, respectively. Similarly, E2, with a dodecyloxy group, exhibited diffraction peaks at 3.1°,
6.1°, and 7.3°, corresponding to d-spacing values of 28.51 Å, 14.50 Å, and 13.12 Å,
respectively. These diffraction patterns and calculated d-spacing values provide insights into
the molecular packing and ordering within the Colh phase. Similarly, material E3 with
hexadecyloxy chain showed three peaks at 2.9°, 5.9°, and 7.1°, and the calculated d-spacing
were 30.49 Å, 14.99 Å, and 13.45 Å, respectively. Compound E4, with an octadecyloxy side
chain, exhibited three distinct diffraction peaks at 2.6°, 4.8°, and 5.3° in the XRD pattern.
The corresponding calculated d-spacing values for these peaks were determined to be 33.99
Å, 18.42 Å, and 16.68 Å, respectively. The observed peak ratio in the diffraction pattern was
found to be 1:1/√3:1/√4. This peak ratio suggests the presence of [100], [110], and [200]
planes in a hexagonal lattice within the Colh type mesophase. The presence of one diffused
peak at 19.7°, 19.8°, 19.9°, and 19.9° in compounds (E1-E4) with d-spacing values 4.56 Å,
4.54 Å, 4.52 Å, and 4.52 Å indicating the liquid like behavior due to lateral interaction of
alkoxy chains. Moreover, in compound E3, one additional diffused peak was found at 24.1°
with a calculated d-spacing of 3.77 Å, this may be due to the presence of molecular
arrangement with π-π stacking due to central functionalized bisphenol A rigid core. The small
angle X-ray diffraction experiment was carried out at room temperature and the measured d-
spacing values in the low angle range were found to be consistent with a hexagonal lattice
structure. Similar diffraction patterns have been found for the Colh type self-assembly in
previous reports [38-40]. The calculated molecular lengths of the bisphenol A-based azo
mesogens (E1-E4) were 26.64 Å, 28.99 Å, 30.32 Å, and 33.82 Å, respectively. These
measured lengths closely align with the calculated molecular lengths of these bent-shaped
molecular systems. Furthermore, the observation of a columnar type liquid crystalline phase
with a broad temperature range for all four azo mesogens is in agreement with the
experimental findings. The POM results, which supported the texture patterns indicative of a

11
Colh phase, are also well corroborated by the XRD investigation. The combination of these
experimental techniques provides strong evidence for the presence of a Colh phase and
supports the conclusion that the synthesized azo mesogens possess liquid crystalline
behavior. The arrangement of molecules in the Colh phase of the azo-linked bi-substituted
bisphenol A mesogen (E1) with tetra-side substitution of decyloxy tail is depicted in Fig. 3.
The proposed molecular arrangement pattern of the azo-based dimers in Colh phase with self-
assembly at room temperature. Additionally, these materials with a bent shape exhibit a wide
array of mesophases and are more stable at lower temperatures and display enhanced thermal
resistance.

Fig. 3. The schematic arrangement of azo mesogen (E1) in columnar hexagonal phase.

3.6 Photophysical properties

The photo-switching properties of the azo-based dimers (E1-E4) were investigated by
preparing their solutions (1.5×10–5 M) in THF solvent. These solutions were then exposed to
UV irradiation to examine the effect of the photoisomerization process. The UV-visible
absorption spectra (Fig. 4) were analyzed to gain a better understanding of the isomerization
process. Bisphenol A substituted azo materials were also examined under UV light for
different time intervals to observe their photo-switching behavior. The spectra exhibited
absorption bands corresponding to π-π* absorption decreases, whereas the n–π* absorption
increases. Further, all four mesogens had similar absorption spectra due to their comparable

12
structural units. Their spectra displayed three absorption peaks, (i) a peak at 250-270 nm, (ii)
a higher energy peak at 375–380 nm, and (iii) a lower energy peak at 460 nm.

Fig. 4. Solutions of compounds E1, E2, E3, and E4 in dilute THF (1.5×10-5 M); UV–visible
absorption (a); fluorescence spectra (b).

The presence of a lower absorption peak at shorter wavelengths indicates the

occurrence of a π–π* transition involving the HOMO (highest occupied molecular orbital)
and LUMO (lowest unoccupied molecular orbital) transitions within the benzene rings [35].
The higher energy peak, spanning a wide range of wavelengths, is attributed to a symmetry
forbidden n –π* transition, indicating the compounds π-electronic nature with charge transfer
characteristics [36]. Among the four azo mesogens, E3 and E4 showed a more pronounced
peak at shorter wavelengths that gradually shifted to longer wavelengths and increased in
terms of absorption compared to the homologues with lower chain substitutions (E1 and E2).
The peak observed at 460 nm corresponds to the n-π* transition (Fig. 4). In the fluorescence
emission spectra, when excited at 397 nm, compounds E1 and E2 exhibited higher intensities
for fluorescence compared to compounds E3 and E4. This difference in intensity can be
attributed to the longer alkoxy chains present in the synthesized compounds. Literature
reports have described azo-based mesogens that demonstrate reversible cis-trans
photoisomerization effects [37-39]. Fig. 5 displays the UV spectrum of two selected
compounds (E1-E2) with different alkoxy tail groups. The fresh solution of the compounds
exhibited a broad band around 380 nm due to the presence of a two-side substituted azo
linking group. Continuous exposure to UV light resulted in the appearance of a low-intensity
band at approximately 462 nm, indicating the transformation of the stable trans isomer to the
unstable cis isomer. When the UV light exposure was turned off, thermal back relaxation
occurred, suggesting the conversion of the unstable cis isomer back to the stable trans isomer
without external influence. Both synthesized bisphenol A based azo mesogens demonstrated

13
similar photosensitive properties. The proposed mechanism involves the transformation of
the stable trans isomer to the unstable cis isomer upon exposure to UV light and subsequent
reversion to the trans isomer when the UV light is no longer present for all the synthesized
compounds (Fig. S18).

Fig. 5. UV/visible absorption spectra of compound E1 (a) and E2 (b) (1.5 × 10-5M); (E1a &
E2a) fresh sample, (E1b & E2b) after exposure at 310-380 nm light for 4.5 hr and (E1c & E2c)
keeping the sample in darkness overnight.
The photoisomerization study of the selected compounds was investigated,
specifically focusing on the impact of exposure to 310-380 nm light for 4.5 hours on the
percentage of cis-absorption in the azo (-N=N-) bond in the respective compound. Fig. S18
expresses in UV irradiation 0 hr, 1 hr, 2 hr, 3 hr, 4 hr, the absorption spectrum. The results
reveal that the peak position and peak shape remain essentially unchanged under different
durations of UV irradiation. However, there is a noticeable variation in peak intensity, which
can be attributed to the cis-trans isomerization of the azo bond (-N=N-) induced by
ultraviolet light. It can be noted that after the ultraviolet irradiation to the solution of the
compound, the absorption intensity at 380 nm increases and gradually decreases at 460 nm.
This indicates a gradual transformation of the cis structure in E1 and E2 into a trans structure
with prolonged exposure to ultraviolet light. As Fig. S18 illustrates, the highest conversion
rate is observed at 4.5 hr and returns to its initial state after 4 hr [40,41]. Furthermore, the
photoisomerization process in compounds E1 and E2 is investigated by the 1H NMR study
before and after the UV irradiation (Fig.S20-21). The complete destabilization of the
aromatic protons after the UV irradiation signifies the formation of cis-isomer from trans-
isomer respectively. In previous report, similar types of study have been carried out to
confirmed the photoisomerization in the azo-based compounds by experimental (1H-NMR)
and DFT study [42, 43].

14
Fig. 6. Proposed mechanism of trans-cis isomerism in bisphenol A derivatives.

4. Conclusions
In summary, we synthesized four derivatives (E1-E4) of bent-shaped LCs using an
azo-ester group linked with bisphenol A and four alkoxy side chains. To assess their
properties, the materials were characterized by various analytical techniques. Specifically,
these compounds displayed a Colh phase with a wide temperature range and demonstrated
thermal stability. To investigate the relationship between structure and properties, the length
of the alkyl chains was varied on the four side arms, ranging from decyl to octadecyl.
Moreover, these materials stabilized the Colh mesophase even at room temperature.
Additionally, it was found that these compounds could undergo a switch from a stable trans
to cis isomer under moderate intensity of UV light.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

Acknowledgment
Authors gratefully acknowledge Department of Chemistry, School of Sciences,
Gujarat University, Ahmedabad for providing necessary lab and infrastructure facility to
carry out this work. Hitendra A. Mali gratefully acknowledges Knowledge Consortium of
Gujarat (KCG), Education Department, Government of Gujarat for Scheme of Developing
High Quality Research (SHODH) fellowship (Student Ref No. 201901380024). Vinay S.
Sharma gratefully acknowledges Human Resource Development Group-Council of Scientific
& Industrial Research (CSIR), New Delhi for Research Associate Fellowship (File No:

15
09/070(0075)/2020-EMR-I). The authors are thankful to the Centre of Excellence, IIT Mandi
for providing analytical and spectral services.

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Graphical Abstract

Declaration of Interests
The authors declare that they have no known competing financial interest or personal
relationships that could have appeared to influence the work reported in this paper.

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