Liquid Crystals

ISSN: 0267-8292 (Print) 1366-5855 (Online) Journal homepage: https://www.tandfonline.com/loi/tlct20

Mesomorphic and DFT diversity of Schiff base

derivatives bearing protruded methoxy groups

Mohamed Hagar, H. A. Ahmed & M. R. Aouad

To cite this article: Mohamed Hagar, H. A. Ahmed & M. R. Aouad (2020): Mesomorphic and
DFT diversity of Schiff base derivatives bearing protruded methoxy groups, Liquid Crystals, DOI:
10.1080/02678292.2020.1764642

To link to this article: https://doi.org/10.1080/02678292.2020.1764642

Published online: 13 May 2020.

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LIQUID CRYSTALS
https://doi.org/10.1080/02678292.2020.1764642

Mesomorphic and DFT diversity of Schiff base derivatives bearing protruded

methoxy groups
a
Mohamed Hagar , H. A. Ahmedb and M. R. Aouadc
a
Faculty of Science, Chemistry Department, Alexandria University, Alexandria, Egypt; bFaculty of Science, Department of Chemistry, Cairo
University, Cairo, Egypt; cChemistry Department, College of Sciences, Al-Madina Al-Munawarah, Taibah University, Al-Madina, Saudi Arabia

ABSTRACT ARTICLE HISTORY

Five three-rings azomethine/ester derivatives, namely, 4-(hexyloxy)phenylazomethine phenyl Received 15 April 2020
benzoate (1), 4ʹ-(4”-hexyloxy)phenylazomethine phenyl-3-methoxy benzoate (2), 4ʹ-(4”-hexyloxy) Accepted 30 April 2020
phenylazomethine phenyl-4-methoxy benzoate (3), 4ʹ-(4”-hexyloxy) phenylazomethine phenyl- KEYWORDS
3,4-dimethoxy benzoate (4), and 4ʹ-(4”-hexyloxy) phenylazomethine phenyl-3,5-dimethoxy benzo- Schiff base liquid crystals;
ate (5), were synthesised and their mesophase behaviour investigated by differential scanning mesomorphic; smectic
calorimetry (DSC) and polarised optical microscopy (POM). Their molecular structures were eluci- A phase; thermal stability;
dated via FT-IR, 1 H-NMR and elemental analysis. All the compounds (1–5) were found to be DFT; molecular geometry
enantiotropically monomorphic possessing SmA phase with high-temperature range and high
thermal stability. Computational studies revealed that all compounds investigated are non-co-
planar. The dipole moment of each derivative is a function of the number of the methoxy groups; it
decreases in the order 2 ˃ 5 ˃ 1 ˃ 3 > 4. On the other hand, the molecular polarisability is
dependent on the number of the methoxy groups, which is accordingly dependent on the
molecular aspect ratio. The results of the FMO calculations revealed that the HOMO orbitals
energies of the methoxy-substituted compounds 2–5 are lower compared to the laterally neat
compound, 1. Finally, the effect of introducing the methoxy group in different position and
number affect the charge distribution that could explain the behaviour of the enhanced
mesophases.

O O
O O
O O

O O
O O O O O O O O

N
N N N N

O
O O O O

1 3 4 5
2

CONTACT Mohamed Hagar [email protected]; H. A. Ahmed [email protected]

© 2020 Informa UK Limited, trading as Taylor & Francis Group
2 M. HAGAR ET AL.

1. Introduction attracts attentions of many researchers [25–33]. In

order to prepare new liquid crystalline compounds
Today, great interests are focused on Schiff bases liquid
with good optical properties, it is worthy to estimate
crystal compounds due to their high thermal stabilities
essential properties such as the energy of the molecular
as thermo-stable mechanisms and corrosion inhibitor
orbitals, the energy gab of the frontier molecular orbi-
systems [1]. The Schiff base linkages maintain the line-
tals, and the structural geometry of such materials.
arity and rigidity of the molecular geometry thus pro-
Generally, the density functional theory (DFT) demon-
moting the mesomorphic stability. The semiconducting
strates to be an effective tool for this kind of estimation
and optically active – CH = N-linking group have also
due to its excellent performance and consistent results.
been widely reported due to the photo efficiency with
In present work, we are going to synthesise and inves-
wavelength dependent on the chemical constituents of
tigate five new three-ring analogous series (1–5) attached
azomethine-containing molecules [2,3]. On the other
via Schiff base and ester central linkages. Hexyloxy group
hand, the ester linkage plays a significant role to impact
is attached to the terminal phenylimine benzoate unit.
the mesophase stability affected by the conjugative
One and/or two methoxy groups are introduced in dif-
interactions between the ester moiety and the phenyl
ferent positions and orientations into the other terminal
rings to which it is attached. Generally, the geometrical
benzene ring aiming to evaluate the effect of the number
shape of an organic compound resulted in a remarkable
and relative positions of methoxy substituents on meso-
change in the mesomorphic properties depending on its
morphic properties. Finally, DFT calculations of the
molecular conformation [4]. In addition to the polarity
thermal parameters, frontier molecular orbitals, as well
and/or polarisability of the molecular cores influence to
as the molecular electrostatic potential, were made to
great extent the stability of the formed mesophase.
explain their mesophase behaviour.
Several low molar mass Schiff base systems and twist-
bend nematic phase have been reported [5–7]. Terminal
substituents (either flexible chains or polar compact 2. Experimental
groups) have essential roles in the phase transition char-
2.1. Materials
acteristics [8]. Recently, Schiff bases are used in new
many applications according to their characteristics 4-methoxybenzoic acid, 3-methoxybenzoic acid,
depend on their structurally different mesogens [9–15]. 3,4-dimethoxybenzoic acid and 3,5-dimethoxybenzoic
Generally, the incorporation of a lateral group into acid were purchased from Sigma Aldrich (Germany).
a rod-shaped molecule increases the breadth of mole- Dichloromethane (DCM), N,N’-
cule, thus leading to reduction of the intermolecular dicyclohexylcarbodiimide (DCC), ethanol and
attraction strength [9]. However, the change of 4-dimethylaminopyridine (DMAP) were purchased
a lateral hydrogen atom by a polar group enhances an from Aldrich (Wisconsin, USA).
additional dipole moment to the molecule. Thus, the
incorporation of a substituent at a side orientation of
2.2. Synthesis
a liquid crystalline compound will have two opposite
impacts: (a) a decrement in the thermal stability of the Compounds 1–5 were prepared according to the follow-
mesophase due to increment of the separation of the ing scheme:
long axes of the molecules [10] and (b) an enhancement
in its polar anisotropy due to its polarising issues. 2.2.1. Synthesis of 4-(4ʹ-hexyloxyphenyl azomethine)
Furthermore, the orientation and the place of the lateral phenol (X)
group are significant due to its effect on the aromatic Equimolar amounts of 4-hydroxybenzaldehyde
conjugation. Moreover, altering the position of the (4.1 mmol) and 4-hexyloxyaniline (790 mg, 4.1 mmol) in
terminal group resulted in the protrusion of the side ethanol (10 ml) were refluxed for 2 h. The reaction mix-
substituent with variable angles. Finally, the effect of the ture was allowed to cool, and the separated product fil-
substituent size is also pronounced [16–24]. In our pre- tered. The obtained solid was recrystallised from ethanol.
vious studies [25,26], some Schiff base/ester systems
were reported aiming to investigate the effect of the 2.2.2. Synthesis of 4ʹ-(4”-hexyloxy phenyl
polarity of terminal substituent, and the location and azomethine phenyl) benzoate and its methoxy-
the orientation of linking groups on the mesophase substituted derivatives (1–5)
behaviour. Molar equivalents of 4-(4ʹ-hexyloxyphenylazomethine)
Interestingly, the computational investigation is an phenol (X) and 3-methoxy, or 4-methoxy or 3,4-or
excellent tool in designing new compounds that and 3,5-dimethoxybenzoic acids (0.01 mole) were dissolved
 LIQUID CRYSTALS 3

R2
R1 R3
OH
COOH
NH2 O H
O O
R3 R1
Ethanol, refulx
+ N R2
O DCC, DMAP, DCM
OH
N
O

1-5
1. R1= H, R2 = H, R3 = H
2. R1= OMe, R2 = H, R3 = H
3. R1= H, R2 = OMe, R3 = H
4. R1= OMe, R2 = OMe, R3 = H
5. R1= OMe, R2 = H, R3 = OMe

Scheme 1. Synthesis of 4ʹ-(4”-hexyloxy phenyl azomethine phenyl) benzoate and its methoxy-substituted derivatives (1–5)..

in dry methylene chloride (DCM) (25 ml). N, N′- (C = N),1574 (C = C), 1466 (C–OAsym), 1260 (C-O
dicyclohexylcarbodiimide (0.02 mol, DCC) and trace Sym).
1
H NMR (850 MHz, CDCl3) δ 10.39 (s, 0.3 H),
amount of 4-dimethylaminopyridine (DMAP) were 10.06 (s, 0.7 H), 8.19 (d, J = 9.6 Hz, 2 H), 8.00 (d,
added to the reaction mixture. The reaction left under J = 8.6 Hz, 2 H), 7.43 (d, J = 8.5 Hz, 2 H), 7.03–6.98
stirring at room temperature for 72 H. The separated (m, 4 H), 6.84 (d, J = 6.7 Hz, 2 H), 4.02–3.82 (m, 5 H,
byproduct was filtered off, the filtrate evaporated, and OCH3, CH3(CH2)3CH2CH2), 1.81–1.63 (m, 2 H,CH3
the obtained product was recrystallised from ethanol. (CH2)3CH2CH2), 1.55–1.10 (m, 6 H, CH3(CH2)3CH2
CH2), 0.91 (t, J = 6.5, 4.1 Hz, 3 H, CH3(CH2)3CH2CH2)
2.2.3. 4-(Hexyloxy)phenylazomethine benzoate (1) . 13 C NMR (214 MHz, CDCl3) δ 191.11, 164.25, 159.52,
Yield: 92%; mp114.0°C, FTIR (ύ, cm−1): 2932–2854 156.94, 156.42, 133.92, 132.50, 131.30, 125.61, 124.40,
(CH2 stretching), 1729 (C = O), 1610 (C = N), 1571 122.66, 121.1, 115.61, 115.32, 114.02, 68.38, 55.61, 31.57,
(C = C), 1452 (C–OAsym), 1241 (C-O Sym). 1 H NMR 29.12, 25.68, 22.61, 14.06. Elemental analyses: Found
(850 MHz, CDCl3) δ 10.39 (s, 0.2 H), 10.09 (s, 0.8 H), (Calc.): C, 75.13 (75.15); H, 6.76 (6.77); N, 3.24 (3.25).
8.24 (d, J = 8.0 Hz, 2 H), 8.01 (d, J = 8.6 Hz, 2 H),
7.70–7.69 (m, 2 H), 7.63–7.54 (m, 2 H), 7.54–7.43 (m, 2.2.5. 4ʹ-(4”-Hexyloxy phenylazomethinephenyl)
2 H), 7.02 (d, J = 8.7 Hz, 2 H), 6.84 (d, J = 8.9 Hz, 2 H), 3,4-methoxy benzoate (4)
3.95 (dt, J = 13.1, 6.6 Hz, 2 H, CH3(CH2)3CH2CH2), Yield: 91%; mp133.0°C, FTIR (ύ, cm−1): FTIR (ύ, cm−1):
1.82–1.63 (m, 2 H,CH3(CH2)3CH2CH2), 1.56–0.99 (m, 2937–2863 (CH2 stretching), 1725 (C = O), 1601
6 H, CH3(CH2)3CH2CH2), 0.91 (t, J = 6.5, 4.1 Hz, 3 H, (C = N), 1572 (C = C), 1465 (C–OAsym), 1264 (C-O
CH3(CH2)3CH2CH2). 13 C NMR (214 MHz, CDCl3) δ Sym).
1
H NMR (850 MHz, CDCl3) δ 1 H NMR
191.07, 164.56, 156.33, 134.09, 131.35, 130.33, 128.77, (850 MHz, CDCl3) δ 10.07 (s, 1 H), 8.01 (d,
125.59, 122.60, 115.46, 68.35, 31.57, 29.18, 25.68, 22.61, J = 8.5 Hz, 2 H), 7.90 (d, J = 8.4, Hz, 2 H), 7.87–7.85
14.06.Elemental analyses: Found (Calc.): C, 77.75 (m, 1 H), 7.71–7.69 (m, 1 H), 7.66 (s, 1 H), 7.54–7.43 (m,
(77.78); H, 6.76 (6.78); N, 3.46 (3.49). 2 H), 7.19–6.98 (m, 2 H), 4.15–3.83 (m, 8 H, 2OCH3,
CH3(CH2)3CH2CH2), 1.89–1.63 (m, 2 H,CH3(CH2)3
2.2.4. 4ʹ-(4”-Hexyloxy phenylazomethinephenyl) CH2CH2), 1.56–0.98 (m, 6 H, CH3(CH2)3CH2CH2),
4-methoxybenzoate (3) 0.97 (t, J = 6.5, 4.1 Hz, 3 H, CH3(CH2)3CH2CH2). 13 C
Yield: 95%; mp120.0°C, FTIR (ύ, cm−1):, FTIR (ύ, cm−1): NMR (214 MHz, CDCl3) δ 191.07, 164.56, 156.33,
2936–2865 (CH2 stretching), 1727 (C = O), 1603 134.09, 131.35, 130.33, 128.77, 125.59, 122.60, 115.46,
4 M. HAGAR ET AL.

68.35, 31.57, 29.18, 25.68, 22.61, 14.06. Elemental ana- polarisation of the ester C = O and – CH = N – groups
lyses: Found (Calc.): C, 72.84 (72.86); H, 6.75 (6.77); N, upon methoxy group inclusion.
3.01 (3.03).

3.2. Mesomorphic behaviour

3. Results and discussion DSC thermograms of the prepared compounds 1 and 3
3.1. Infrared absorption spectra of components 1-5 during heating/cooling cycles are given as examples in
Figure 1. As shown from Figure 1, both compounds
IR spectra, 1H NMR, and elemental analyses for the showed two endotherms peaks of the crystal–SmA
compounds prepared were consistent with the assigned phase and SmA phase–isotropic transitions upon heating.
structures. The results of FT-IR showed that the posi- Also, upon cooling cycle, the compounds exhibit the
tion and the number of the methoxy groups extensively SmA phase as the only mesophase. The POM showed
affect the position of the characteristic bands of the focal conic fan characteristic for the SmA phase (Figure
main distinctive functional groups.
2). This indicates that these compounds exhibit enantio-
This effect is pronounced on the C = O and CH = N tropic monomorphic properties. Data in details of the
groups. The effect of the position of methoxy groups transition temperatures and their associated enthalpy of
and their numbers on the C = O absorption band the all prepared analogues 1–5 series, all bearing same
increases by 12 cm−1 (1727 cm−1 for mono para meth- terminal alkoxy-chain length (n = 6), as estimated from
oxy-substituted derivative and 1739 cm−1 for meta deri- DSC measurements, are collected in Table 1. Graphical
vative). On the other hand, the CH = N band increases representation of transition temperatures is depicted in
by 10 cm−1(1603–1611 cm−1), moreover, these func- Figure 3 in order to evaluate the effect of position and
tional groups of 3,5-dimethoxy derivative have higher number of methoxy groups on the mesophase behaviour.
vibrational frequency than that of the 3,4-dimethoxy As estimated from Table 1 and Figure 3, the melting
derivative. These results revealed that the position and temperatures (Cr–SmA) of derivatives decreasing in order
number of the methoxy groups extensively affects the 4 > 5 > 3 > 1 > 2. On the other hand, all the members are
polar nature of the molecules as a difference on the enantiotropic smectogenic with high thermal SmA stability

Figure 1. (Colour online) DSC thermograms of (a) compound 1 and (b) compound 3 upon heating and cooling scans with heating rate
10°C/min.

Figure 2. (Colour online) SmA textures under POM upon heating for (a) compound 1 at 112.0°C and (b) compound 3 at 220.0°C.
 LIQUID CRYSTALS 5

Table 1. Phase transition temperatures (T, °C), enthalpy of transi- decreases in the following order: 3 > 2 > 5 > 4 > 1, while
tions (ΔH, kJ/mol) and normalised transition entropy (ΔS/R) for its mesophase range (ΔTSmA) decreases in the order:
compounds 1–5. 3 > 2 > 5 > 1 > 4. The highest SmA stability and range of
Compound TCr-SmA ΔHCr-SmA TSmA-I ΔHSmA-I ΔSSmA-I/R
compound 3, since the – OCH3 group is attached to posi-
1 113.9 36.39 158.1 0.95 0.26
2 85.3 28.03 199.4 1.87 0.48 tion-4 with respect to the ester linkage. Thus, in our inves-
3 119.6 40.83 255.6 1.37 0.31 tigated compounds, upon para substitution (in position-4),
4 132.8 38.34 158.9 1.35 0.38
5 120.4 47.72 196.1 1.51 0.39 the electron-donating substituent (OCH3) is accompanied
Cr-SmA, crystal to smectic A transition; SmA-I, Smectic A to isotropic liquid with an increment in the dipole moment; such enhanced
transition. dipole is expected to induce high stability to the mesophase.
Similar observations have been made for other liquid crys-
and wide mesomorphic temperature range. Comparison tals and have been accounted for in terms of a change of
was made first between positional isomers 2 (i.e. OCH3- shape on substituting the mesogenic unit rather than from
group in position-3) and its isomer 3 (i.e. OCH3- group in any significant enhancement of the shape anisotropy [34].
position-4). Results revealed that the thermal stability of the Generally, the polarity of the attached groups, polarisabil-
SmA phase is dependent on the enhanced dipole of the ity, aspect ratio, rigidity and architecture of the molecule
mesogenic core of the molecule which is remarkably are considered significant parameters that could be respon-
dependent on the position of methoxy group. Another sible for the stability of the formed mesophases and the type
factor is the molecular geometry which again varies accord- of their textures. These factors share in different magnitude
ing to the location of the substituent (OCH3). Mesomeric to the mesophase behaviour. It is well known that the
interactions of the methoxy group in the positional isomers stability of a mesophase of a given liquid crystalline com-
2 and 3 with the ester C = O group are prohibited to the pounds is enhanced by any increment in the polarity and/
extent that the derivatives possess high thermal stability or polarisability of the mesogenic core of the materials,
than the unsubstituted analogue (1). A second comparison which is impacted by the polarity of the attached substitu-
was made between the di-methoxy substituted positional ent that would resulted in changing the polarity of mole-
isomers 4 and 5. The two methoxy groups in compound 4 cules. Further, a strong van der Waals attractions, which
are introduced in positions −3 and −4 with respect to the enhanced by the increasing of the terminal alkoxy length,
ester – OCO-group, while in compound 5 the two methoxy enhances the mesophase stability of the SmA phase by
groups are located into position −3 and −5. The thermal supporting the lamellar packing. On the other hand, it
stability of di-laterally substituted isomer 5 is higher than its suppresses the nematic phase range. Furthermore, the
corresponding isomer 4, this may be attributed to the high SmA range (ΔTSmA = TSmA-Tcr) is increased from 114.1
molecular mesomeric interactions. The thermal stability of (compound 2) to 136.0°C (compound 3) with changing the
SmA phase (SmA-isotropic transition) was found to position of -OCH3 group from meta to para-position with

Figure 3. (Colour online) DSC graphical transitions of series 1–5 upon heating.
6 M. HAGAR ET AL.

respect to the ester group. Also, the range (ΔTSmA) crystalline matter, the lowest energy may be different and
increases from 26.0°C to 75.7°C as the orientations of the more elongated species will be preferred [42].
two methoxy groups changed from positions 3 and 4 The results of the theoretical DFT calculations for all
(compound 4) to positions 3 and 5 (compound 5) with studied compounds revealed the non-co-planarity of the
respect to the ester unit. Compared with compound 1, three rings A, B and C. The angle between the plane passing
substitution on the terminal phenyl ring, attached to car- through the ring A and the plane passing through the ring
bonyl group, changed from mono-OCH3-substituted to di- B is θ = 40.5º, 37.8º, 36.7º, 40.1º, and 36.6º for compounds
OCH3-substituted ring. For all derivatives, it was observed 1–5, respectively. However, the twist angle between the
that, irrespective of the polarity of alkoxy chain, the orien- planes passing through the ring B and C is θ ≈ 37.5º for
tation and position of methoxy groups and their electronic all compounds regardless of the type or the number of the
interactions with the remainder of the molecule enhance attached methoxy groups, Figure 4. The presence of the
the mesophase properties. Further, It was observed that the electron-donating OCH3-groups on the carboxylate ring of
un-substituted compound 1 has the lowest clearing tem- the ester increases the co-planarity of all compounds except
peratures (Tc); this can be interpreted in terms of the for the 3,4-di-methoxy derivative (4); this could be attrib-
reduction of length-to-breadth ratio as a result of their uted to the steric hindrance of the two methoxy groups that
least anisotropic in terms of their shape and this enhances could encounter their resonance effect.
molecular biaxiality [34–37]. The dipole moments and polarisability of the prepared
compounds are given in Table 2. It is observed that dipole
The entropy change accompanying the SmA phase tran- moment decreases in the order 2 ˃ 5 ˃ 1 ˃ 3 > 4. The
sitions (ΔSSmA-I/R) were estimated for the investigated
compounds and tabulated in Table 1. An irregular trend
highest dipole moment of the 3-methoxy derivative, 2,
and small magnitudes of the entropy changes are could be attributed to the presence of oxygen atom of the
observed. All estimated entropy changes are low values high electronegative OCH3- group which is not in the same
for conventional low molar mass mesogens and this may axis of the other terminal hexyloxy group. Significantly, the
be attributed to the thermal cis-trans isomerization of the attachment of the methoxy group in the para position with
linkage and this is in agreement with previous report
respect to the ester group decreases the dipole moment
[38]. Besides, another factor could encourage this obser-
vations is the molecular biaxiality that is induced by the value to μ = 2.7 Debye. However, the steric hindrance of the
lateral groups (in compounds 2, 4 and 5) and the rela- di-methoxy groups in 4 could illustrate the decrease of the
tively high values of clearing temperatures, which in turn dipole moment to value, μ = 2.4 Debye. Moreover, the
reduces the entropy changes [39–41]. symmetry of the electron donation of the two OCH3-
groups in 5 which are not co-axial with the para hexyloxy
group increases the dipole moment to, μ = 2.4 Debye. In
addition, the position and number of the methoxy groups
3.3. DFT calculations
have a significant effect on the polarisability. The polarisa-
The theoretical DFT estimations were carried by DFT/ bility of the materials shows how is the susceptibility of
B3LYP method at 6–31 G (d,p) basis set in the gas phase. molecular system electron cloud how to be affected under
The predicted total energies, dipole moments, and thermo- the approaching of a charge, since it depends on the com-
dynamic parameters of the prepared compounds are tabu- plexity of the compounds as well as the size of the mole-
lated in Table 2. All optimised structures of compounds cular structure. Molecules of the large size are more
1–5 are proved to be stable due to the absence of the polarisable than the smaller ones. It is worthy noticed that
imaginary frequency. It is worthy to note that although the unsubstituted compound, 1, is the smallest in size and it
these calculations will provide a prediction of the preferred is the least polarisability, α = 357.16 Bohr3; however, the
molecular geometry in the gas phase, the presence of these attachment of the methoxy group at the meta position (2)
compounds in a condensed phase such as a liquid increases the polarisability to 380.64 Bohr3. On the other

Table 2. Thermal parameters (Hartree/Particle), Polarisability α and Dipole Moment (Debye) of 1–5.
Parameter 1 2 3 4 5
Ecorr 0.473228 0.502758 0.502915 0.534663 0.534842
ZPVE −1286.939383 −1401.838984 −1401.841809 −1516.355621 −1516.359380
Etot −1286.911278 −1401.808158 −1401.811010 −1516.321880 −1516.325855
H −1286.910334 −1401.807214 −1401.810066 −1516.320936 −1516.324911
G −1287.005502 −1401.907374 −1401.910148 −1516.428258 −1516.431261
Total Dipole Moment 3.0375 3.7849 2.6744 2.4264 3.2840
Polarisability α 357.16 380.64 384.10 402.11 399.67
ZPVE, Sum of electronic and zero-point energies; Etot, Sum of electronic and thermal energies; H, Sum of electronic and thermal enthalpies; G, Sum of
electronic and thermal free energies.
 LIQUID CRYSTALS 7

Figure 4. (Colour online) Optimised geometrical structures of compounds 1–5.

hand, the para position of the methoxy group (in 3) of orderness and increases the lateral attraction to enhance
increases the polarisability by 4.00 Bohr3 with respect to the smectic mesophase rather than the less ordered nematic
the meta one. When the length of the para-substituted phase. The high dipole moment of compound 2 with high
compound will be longer than the length of meta substi- polarisability (3.8 Debye and 380 Bohr3) could be an expla-
tuted one, with lower width of the later compared to the nation of the high mesophase range ≈ 114oC. On the other
former, hence the aspect ratio of compound 3 is higher hand, the higher aspect ratio and polarisability with the
than 2, and this could illustrate the higher value of com- decrement of the dipole moment significantly increases the
pounds 3 and 4 with respect to the their corresponding range to ≈ 136°C. It is worthy noted that high decrement of
isomers 2 and 5. The change of the dipole moment and the the polarity and the aspect ratio of compound 4 to 2.4
polarisability are excellent explanation for the experimental Debye and 3.5 have a negative effect on the mesophase
thermal results. The higher dipole moment and polarisa- range to be ≈ 26oC compared to its isomer 5, mesophase
bility of the prepared compounds permits the high degree range ≈ 76°C, µ = 3.2 Debye (Figure 5 and Table 3).

Figure 5. The dependence of mesophase stability and its range on the dipole moment, aspect ratio and polarisability.
8 M. HAGAR ET AL.

Table 3. The dimension parameters of the investigated com- electrostatic potential (MEP) is a useful tool to study
pounds 1–5. the reactivity of the prepared compounds towards
Parameter 1 2 3 4 5 electrophilic and nucleophilic attacks. Moreover,
Length (L) Å 28.6 29.7 30.3 30.1 29.8
Width (D) Å 7.8 8.3 8.1 8.4 9.4
recently, our group has found a relationship between
Aspect ratio (L/D) 3.667 3.578 3.741 3.583 3.170 the charge distribution and the type and the nature of
Area (L*D) Å2 223.08 246.51 245.43 252.84 280.12 the mesophase [43–47]. In the most of MEPs, the
maximum negative region which preferred site for
3.3.1 Frontier molecular orbitals electrophilic attack indicated as red colour. As shown
Frontier molecular orbitals (FMOs) are the highest in Figure 7, the most negatively charged centre is the
occupied molecular orbital (HOMO) and the lowest carbonyl oxygen of the ester moiety. On the other
unoccupied molecular orbital (LUMO). The HOMO is hand, the hexyloxy group is the most positive region.
the highest energy orbital occupied with electrons, so it The phenyl benzoate group that is blue for the alky-
is an electron donor, while, LUMO is the lowest energy lated neat carries red character by attachment of the
orbital that has the space to accept electrons, so it is an methoxy groups. The difference of the charge distribu-
electron acceptor. The frontier molecular orbitals tion by changing the number and the location of the
(FMO) can offer a reasonable qualitative prediction of methoxy groups is an excellent explanation on the
the excitation properties and the ability of electron divers of the property of the mesophases.
transport. Moreover, HOMO and LUMO are very The high degree of charge distribution over the whole
important quantum chemical parameters to determine of the prepared compounds permits the high degree of
the reactivity of the molecules. The energies of the the lateral attraction to enhance the ordered smectic
HOMO and LUMO orbitals of the studied compounds mesophase rather than the less ordered nematic meso-
were calculated using DFT/B3LYP (d,p) method and the phase. Moreover, the electron donation at the position 4
results are tabulated in Table 4. The results of the FMO (compound 3) changes the charge distribution to
energy analysis revealed that the energies of HOMO enhance the mesophase stability to TSmA-I = 255°C with
orbitals of the alkylated compounds 2–5 are lower in respect to 199°C of that possessing the methoxy group at
energy compared to the unsubstituted compound, 1. position 3 (compound 2). However, the steric effect of
However, the attachment of the methoxy groups lowers the methoxy groups of the 3,4-dimethoxy derivative (4)
the HOMO and LUMO levels and this could be attrib- decreases the mesophase range and stability compared to
uted to the extra-conjugation of the π-system due to the its corresponding isomer 3,5-dimethoxy derivative 5.
resonance effect of the methoxy groups. The isodensity
surface plots of HOMO and LUMO for investigated 3.3.3. Structurally different isomers comparison
compounds are shown in Figure 6. The electron density When the present prepared compound 3 is compared
of HOMO of all compounds is localised on the benzoate with that previously reported corresponding isomer, 4–
ring; however, it shifts to the phenylazomethine ring for ((4ʹ–methoxyphenylimino) methyl)phenyl 4”–hexyloxy-
the LUMO. The attachment of the highly electron- benzoates (6) [48], the two isomeric compounds that
donating methoxy groups increases the softness of the differ from each other in the position of the terminal
compounds. However, the positions 3 and 5 have more groups (CH3O and C6H13O), it is found that the meso-
pronounced impacts on the softness than the 4-position. morphic stabilities of the two isomers 3 and 6 are rela-
tively similar. While, their types and ranges of formed
mesophase are different. The present investigated com-
3.3.2. Molecular electrostatic potential (MEP) pound 3 is purely smectogenic exhibiting a wide SmA
The molecular electrostatic potential of the studied temperature range (136.0°C), while its corresponding
compounds (1–5) is given in Figure 7. The molecular isomer 6 is purely nematogenic possessing broad
N range (156.0°C). That may be ascribed to the presence
of the long hexyloxy group near to the carboxylate group
Table 4. Molecular orbital energies and global softness (S) of
(COO) (6) it enhances the end – end interaction to
1–5.
ΔE(ELUMO
afford the less ordered nematic phase. However, in the
EHOMO ELUMO -EHOMO) other positional isomer 3 the molecular structure facil-
Compound (a.u) (a.u) (a.u) S = 1/ΔE = (1/2η) itates the parallel as well as terminal aggregation to
1 −0.210980 −0.06759 0.1434 6.9740
2 −0.205727 −0.06731 0.1384 7.2245
certain extent that enhances the more ordered SmA
3 −0.20449 −0.06385 0.1406 7.1104 mesophase. On the other hand, the position of the longer
4 −0.20440 −0.06358 0.1408 7.1013 chain hexyloxy group, does not affect neither the transi-
5 −0.20410 −0.06482 0.1393 7.1798
tion temperature nor its range, Figure 8.
 LIQUID CRYSTALS 9

Figure 6. (Colour online) The calculated ground state isodensity surface plots for FMOs of 1–5.

Figure 7. (Colour online) Molecular electrostatic potentials (MEP) of compounds 1–5.

When comparison is made for the mesophase stabi- stereo conformation of the molecule. In the present
lity, polarisability, molecular dipole moment, aspect series of compounds, 1–5, the association of the rod-
ratio and co-planarity angle between the five analogous like molecules, and consequently their mesophases sta-
compounds 1–5, they were found to decreases in the bilities depend mainly on several factors, namely: 1.
following order: Lateral adhesion of linear molecules that increases with
It is well known that the mesophase characteristics of the increase of the alkoxy-chain length (n) or aspect
a certain liquid crystal molecule depend mainly on inter ratio. 2. Molecular geometry which varies according the
molecular interactions, mesomeric properties, and the co-planarity angle. 3. The steric effect of the laterally
protruded substituent that differs according to its posi-
Mesophase thermal 3>2>5>4>1
stability, (255.6) (199.4) (196.1) (158.9) (158.1) tion and orientation. 4. End-to-end interaction that var-
Polarisability, 4>5>3>2>1 ies according to the polarity of the terminal substituent,
(402.11) (399.67) (384.10) (380.64) and consequently the polarisability of the whole mole-
(357.16)
Total dipole moment, 2>5>1>3>4
cule. The azomethine/ester linking groups allow the con-
(3.785) (3.284) (3.038) (2.674) (2.426) jugation within the whole mesogenic core of the
Aspect ratio (L/D), 3>1>4>2>5 molecule, thus preventing the twist bend. Comparing
(3.741) (3.667) (3.583) (3.578) (3.170)
the SmA stability of analogues of 1–5, as given above,
Co-planarity (angle), 1>4>2>3≈5
(40.5 o) (40.1 o) (37.8 o) (36.7 o) (36.6 o) indicates that all of the four parameters (Polarity, polari-
sability, aspect ratio, or co-planarity, do not have similar
10 M. HAGAR ET AL.

4. Conclusion
Five three-rings azomethine/ester liquid crystalline
compounds, namely, 4-(hexyloxy)phenylazomethine
phenyl benzoate (1), 4ʹ-(4”-hexyloxy)phenylazomethine
phenyl-3-methoxy benzoate (2), 4ʹ-(4”-hexyloxy)phe-
nylazomethine phenyl-4-methoxy benzoate (3), 4ʹ-(4”-
hexyloxy) phenylazomethine phenyl-3,4-dimethoxy
benzoate (4), and 4ʹ-(4”-hexyloxy) phenylazomethine
phenyl-3,5-dimethoxy benzoate (5), were prepared.
The following results have been concluded:

● All investigated compounds are enantiotropic

monomorphic possessing broad smectic A (SmA)
mesophase range with high thermal stability.
● The position and number of the attached methoxy
groups are more effective on the mesomorphic
characterisations.
● The dipole moment is affected by the number of
the methoxy group and it decreases in the order 2 ˃
5 ˃ 1 ˃ 3 > 4.
● The molecular polarisability is affected by the num-
ber of the methoxy groups as it depends on the
molecular aspect ratios.
● The effect the charge distribution orientation by
changing the number and position of the methoxy
groups explain the mesophases behaviour.
● Polarity, polarisability, aspect ratio, or co-
planarity, do not have similar effects on the meso-
phase behaviour.
● Finally, the orientation of the two terminals (CH3
O and C6H13O) of one of our investigated com-
Figure 8. Positional isomers 4-((4ʹ-hexyloxyphenylimino)methyl) pounds and its positional isomer affect the type of
phenyl 4”-methoxybenzoate (3) and 4–((4ʹ–methoxyphenyli- the observed mesophase regardless to neither the
mino)methyl)phenyl 4”–hexyloxybenzoate (6). transition temperature nor its range.
effects on the mesophase behaviour in these five investi-
gated compounds). From these comparisons it is shown
Disclosure statement
that the co-planarity angles vary slightly between 36.6°
and 40.5°, the dipole moment varies effectively between No potential conflict of interest was reported by the author.
2.4 and 3.79 D, and similarly the polarisability varies
widely between 402 and 457 Bohr3.
The similarity in clearing temperatures between 2 ORCID
and 5 may be attributed to the rapid rotation about
Mohamed Hagar http://orcid.org/0000-0003-0169-7738
the molecular long axis in the SmA phase and so the
excluded volumes of the molecules that in agreement
with the previous findings [49]. However, one of the
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