Journal of Molecular Liquids 332 (2021) 115879

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Exceptional dual fluorescent, excited-state intramolecular

proton-transfer (ESIPT) columnar liquid crystals characterized
by J-stacking and large Stokes shifts
Madhu Babu Kanakala, Channabasaveshwar V. Yelamaggad ⁎
Centre for Nano and Soft Matter Sciences(CeNS), Arkavathi, Shivanapura, Dasanapura Hobli, Bangalore - 562162, India

a r t i c l e i n f o a b s t r a c t

Article history: Excited-State Intramolecular Proton-Transfer (ESIPT) fluorophores are emerging as promising future materials
Received 18 December 2020 for electronic and biotechnological applications. ESIPT columnar (Col) liquid crystals (LCs) have been especially
Received in revised form 3 March 2021 projected as the apt materials for advanced technological endeavors. But, there are hardly any explorations in this
Accepted 8 March 2021
direction and thus, needing immediate attention. Herein we report on the synthesis, characterization, and ESIPT
Available online 11 March 2021
activity of a homologous series of novel phasmidic bis(N-salicylideneaniline) Col LCs. Optical microscopic, calo-
Keywords:
rimetric and powder X-ray diffraction (XRD) studies evidence the occurrence of hexagonal columnar (Colh)
Phasmids phase having p6mm symmetry where the constituent slices result from the self-assembly of a pair of mesogens
Columar hexagonal phase in a side-by-side manner facilitated by intense longitudinal π-π interactions. X-ray data confirm the absence of
ESIPT activity both directionally correlated tilting of the slices and transverse core-core interactions within the columns. Fluo-
Dual-fluorescence rescence probing clearly evidence the ESIPT occurring not only in DCM solution of the mesogens but also in their
J-aggregates three-condensed states viz., solid, liquid crystal, and isotropic liquid phase; in general, two archetypal emission
bands at ~430 nm (weak) and ~ 630 nm (strong) with large Stokes shifts (250–275 nm) of ESIPT phenomenon
have been observed. The slow shift of emission maxima of the ESIPT fluorescence as a function of decreasing tem-
perature without photoluminescence quenching coupled with the estimated tilt angle (ϴ) of the slices normal to
the columnar axis (37 to 42o), from the XRD data, confirm the formation of so-called Scheibe or J-aggregates. The
redox activity, metal ion sensing ability, and solvatochromism of the mesogens have also been investigated. The
study suggests that these ESIPT Col LCs with band-gap of about 3 eV can be regarded as wide-bandgap semicon-
ducting materials having the electronic characteristics falling between those of conventional semiconductors and
insulators.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction also structural defect eliminating property through the natural self-
healing process. It has been well demonstrated over the years that the
Functional materials belong to a special class of man-made sub- exceptional characteristics of LCs, which were so far associated mainly
stances that are mostly organic or inorganic or hybrid/composite sub- with the LC display technology, can be well-exploited in devices such
stances ranging from small molecular (low molar mass) compounds as semiconductors, sensors, elastomer actuators, photovoltaics, organic
to polymers. [1–9] They, being hard [1–8] or soft [9] in nature, possess light-emitting diodes (OLEDs), organic field-effect transistors (OFETs),
the ability to display predetermined physicochemical properties/phe- etc. [11,13,14]
nomenon under the influence of an external stimulus such as light, tem- For example, such technological endeavors are attainable by utiliz-
perature, sound, electric field, magnetic field, mechanical stress, ing the exceptional characteristics of columnar (Col) LC phases formed
substrate surface anchoring conditions, etc. Among wide varieties of by the parallel packing of infinitely long columns organized in two-
soft functional materials reported hitherto, liquid crystals (LCs) have se- dimensional (2D) lattices; their intrinsic electronic features originate
cured a prominent position in materials science encompassing the as- purely from the disk-like (discotic) aromatic or heteroaromatic cores,
pects of both basic research and applied science. [10–12] They are substituted peripherally with three to several flexible aliphatic tails,
self-organized fluid (soft) superstructures and thus, possess the inher- stacked co-facially in columns through intense π-π associations/interac-
ent ability of not only responding to the aforesaid external stimuli but tions. [15–21] While the insulating alkyl chains prevent the closer inter-
columnar interactions, the π-π interaction of discotic mesogens in each
⁎ Corresponding author. column creates 1D charge carrier pathway along the long column axis.
E-mail address: [email protected] (C.V. Yelamaggad). The average π-π stacking distance of the discotic cores in a column is

https://doi.org/10.1016/j.molliq.2021.115879
0167-7322/© 2021 Elsevier B.V. All rights reserved.
M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

typically of the order of 3.5 Å, and thus, an overlap of the π-π* lowest un- Among the various types of ESIPT active molecules reported hitherto,
occupied molecular orbitals (LUMOs) should be possible. [16,17,21] [43,44,66–73] salicylideneanilines attracted our attention owing to
Thus, the Col phases, which have been aptly regarded as molecular their potential for various technological endeavors. [67] In particular,
wires or quasi-one-dimensional (Q1D) conductors, hold huge promise the investigations on phasmidic LCs by Hiremath [43,44] clearly hinted
for the field of organic electronics due to their intrinsic ability to serve that the mesomoprism can be induced in bis(N-salicylideneaniline)s
as the active media, in the form of thin-films, to perform the essential (BSANs). It was observed in this detailed study that out of the three con-
functions such as carrier-injection or blocking, and electron-hole re- stitutional isomeric bis(N-salicylideneaniline)s, viz., BSAN-I, BSAN-II &
combination or separation. [16–21] However, in recent years, consider- BSAN-III (Fig. 1), the isomers belonging to BSAN-I category derived
able efforts have been devoted not only to control the vital parameters from 3,6-diformylcatechol shows columnar behavior. These conformers
such as oxidation potential and electron affinity but also to incorporate (BSAN-I) can undergo a reversible proton-transfer process to furnish
the light absorption and luminescent properties to enable Col phase to two tautomers, namely, enol-imine (OH) (BSAN-I(OH)), and keto-
serve as the emissive layers. [16–22] Thus, fluorescent Col LCs have enamine (NH) (BSAN-I(NH)) forms (Fig. 1). That is, these compounds
not only the ability to replace light-emitting amorphous/crystalline have the intrinsic ability to display ESIPT fluorescence owing to their
solids [23–25] but also possess promising technological aspects such novel structural composition where the intramolecular hydrogen (H)-
as long-range order [16], charge-transport property / anisotropic con- bonding correlation among a hydrogen bond donor (–OH) group and
ductivity, [16,19,26] long exciton diffusion lengths, [27,28] self-healing a hydrogen bond acceptor (-C=N, imine) linking group exists. Despite
ability [ 16,17], low-cost solution processability [16] etc. The Col phases these exciting feature, the investigations on the photophysical proper-
are generally classified, depending upon the degree of order in the mo- ties of BSAN-I columnar LCs have not been revealed hitherto. Thus, we
lecular stacking, the alignment of the discogens along the columnar axis, set out our goal to realize the analogs of BSAN-I hexacatenars and eval-
and the symmetry of the 2D lattice, into seven different classes. Of these, uate their ESIPT activity. Herein, we report on the synthesis and detailed
Col hexagonal (Colh) and/or Col rectangular (Colr) phases are often en- characterization of a series of ESIPT active phasmidic bis(N-
countered in many discotic LCs. [16,17] While four different lattice sym- salicylideneaniline)s (PBSANs) existing in Enol-Imine form, which
metries viz., p2mm, c2mm, p2gg, and p2mg are assigned for the Colr upon photoexcitation transforms into Keto-Enamaine tautomeric form
phase, the Colh phase, wherein the columns are arranged on a 2D- (Fig. 1).
hexagonal lattice, is generally described by the plane group p6mm. [16]
As is well known, a special type of Colh phase is formed by the self-
assembly of simple non-discoid LCs, called phasmidic or polycatenar 2. Results and discussion
mesogens. They comprise a long rod-like core ending on either side
with lipophilic segments comprising two or three flexible tails. 2.1. Synthesis and characterization
[12,16,29–44] They have been categorized according to the total num-
ber of n-alkoxy tails they possess; for example, polycatenars substituted The conventional synthetic steps employed for the preparation
with four, five and six terminal paraffinic tails have been respectively re- of target PBSAN materials have been outlined in Scheme 1. Gallic
ferred to as tetracatenars, pentacatenars and hexacatenars [ 29–32]. acid was treated with ethanol in the presence of an acid catalyst
These relatively new class of thermotropic LCs bridge the gap between to obtain ethylgallate (1) [51], which was subjected to O-alkylation
conventional rod-like and disk-shaped LC molecular architectures, and with n-alkylbromides under the reaction conditions of Williamson
thus, they exhibit a rich polymesomorphism. That is, experimentally, ether synthesis protocol to get ethyl 3,4,5-tris(n-alkyloxy)benzoates
it has been evidenced that these hybrid mesogens not only show the ne- (2a-j) [52]. Alkaline hydrolysis of esters 2a-j using aqueous sodium
matic (N), smectic (lamellar) as well as bicontinuous/micellar cubic, te- hydroxide (5%) in ethanol provided the corresponding 3,4,5-tris
tragonal and orthorhombic three-dimensional phases but also stabilize (n-alkyloxy)benzoic acids (3a-j) [53] which were esterfied with 4-
a unique Colh phase in a series of compounds or pure material. nitrophenol in the presence of N,N′-dicyclohexylcarbodiimide (DCC)
[12,16,29–33] However, such phase transitional behavior largely de- and 4-(dimethylamino)pyridine (DMAP) to obtain 4-nitrophenyl
pends on the number of alkoxy tails they possess on either side of the 3,4,5-tris(n-alkyloxy)benzoates (4a-j) [53]. Hydrogenation of these
central calamitic core. Of the variety of polycatenar LCs reported hith- nitro compounds 4a-j in the presence of Pd\\C (10%) and under hydro-
erto, the hexacatenars (phasmids) have been attracting attention not gen (H2) balloon (1 atm) conditions afforded 4-aminophenyl 3,4,5-tris
only because of their inherent ability to self-assemble into Col phase (n-alkyloxy)benzoates (5a-j) [54]. The central core of the target phas-
but also they provide the opportunity to incorporate functional charac- mids namely 2,3-dihydroxyterephthalaldehyde (7) was synthesized
teristics through the selection of predetermined molecular structural starting from 1,2-dimethoxybenzene. It was subjected to lithiation
segments. Thus, a wide variety of functional phasmids have been real- using n-butyllithium (n-BuLi) in the presence of tetramethylethylenedi-
ized, which include heterocycles, [33–38] metallomesogens, [38] ionic amine (TMEDA), and the treatment of mettallated intermediate with N,
LCs, [40,41] photo-responsive mesogens, [42] intra-molecular H- N-dimethylformamide (DMF) yielded 2,3-dimethoxyterephthala-
bonded systems, [43,44] thermochromic LCs, [45] bent-core com- ldehyde (6). [55]
pounds, [46,47] fluorescent materials etc. [48–64] O-Demethylation facilitated by boron tribromide (BBr3) of com-
However, the fluorescent phasmidics, owing to their technological pound 6 afforded the vital intermediate 7. [56,57] Finally, an acid-
relevance, have been studied intensively through the rational design catalyzed condensation of amines (5a-j) with aldehyde 7 afforded the
and synthesis of diverse series of materials derived from functional desired materials in good yields (69–75%). The molecular structures of
fluorophores [48–65]. Of these, there has been a thought-provoking all synthesized liquid crystals were ascertained unambiguously using
work by Park and co-workers reporting that phasmidic LCs, possessing the data derived from spectroscopic techniques viz., UV–visible, FTIR,
1
intra-molecular proton-transfer (ESIPT) activity, form tilted (J-type) H NMR & 13C NMR, see Figs. S3 to S20 of supporting information (SI),
stacking in the column of the LC phases; interestingly, this assembly and elemental analyses. These characterization data, along with the syn-
augments the fluorescence emission of the mesophase with a quantum thetic procedure of these final mesogens, are given in the experimental
yield of 34% and a large Stokes' shift (173 nm) [ 65]. It is speculated that section (II.5). However, the intermediates, 2a-j, 3a-j, 4a-j, 5a-j, 6 & 7, ac-
the ESIPT fluorescence coupled with Col behavior make the phasmidics complished here are known compounds 51–57, and they have been ex-
ideal candidates for applications in emissive LCDs, polarized organic la- amined for their molecular structures with the aid of FTIR, 1H NMR,
sers and anisotropic OLEDs. [34,65] Thus, we became interested in and elemental analyses only. The synthetic procedures and characteri-
working on this topic of research and accordingly, searched for the zation data of these precursors have been presented in supporting
ESIPT active molecules for incorporating Col mesomorphic behavior. information (SI).

2
M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

Fig. 1. Skeletal structures of the previously studied hexacatenar LCs (BSAN-I, II & III; Refs. 43 & 44) - the source of present work. Structures of the phasmidic bis(N-salicylideneaniline)s,
(PBSANs) investigated in the present work.

2.2. Thermal properties and mesomorphic behavior characteristically displaying a fluid and homogeneous birefringent tex-
ture that remains unaltered until the isotropization temperature. The
The thermal and mesomorphic properties of the newly synthesized fluidity of the phase was evident from the fact that the coverslip of the
PBSAN materials were evaluated by a combination of polarizing optical specimen could be moved with great ease using a pair of tongue or a
microscopy (POM), differential scanning calorimetry (DSC), and paper pin. Upon cooling, a transition from the isotropic liquid state
variable-temperature X-ray diffraction (XRD). To figure out the phase into mesophase occurs, with the texture showing typical defects associ-
transitions/temperatures, a minute quantity (~1 mg) of the pristine ated with the Colh phase.
sample, held between a glass slide and a coverslip, was subjected to re- The optical texture of the Col phase appears to vary notably from one
peated heating-cooling scans using a hot stage and viewed under POM. homolog to another. For example, as shown in Figs. 2a-c, the POM tex-
DSC thermograms for the heating-cooling scans of the mesogens were tures of the Col phase formed by mesogens PBSAN-10, PBSAN-11, and
recorded at a rate of 5 °C / min to confirm the transition temperatures PBSAN-14 differ considerably from each other. The texture of the Col
and enthalpy changes of phase transitions. The data derived from phase, emanating from the dark background of isotropic liquid of com-
these studies are given in Table 1. It is apparent from the collected pound PBSAN-10, appears initially as tiny batonnets that eventually co-
data that the first (lowest) member of the series is non-mesomorphic, alesces to a pseudo focal-conic fan-like texture as shown in Fig. 2a. The
whereas the remaining members are liquid crystalline exhibiting an Col phases formed while cooling from the isotropic phase of
identical, thermodynamically stable mesophase. Upon heating, the pris- PBSAN-11 and PBSAN-14 exhibit pseudo-isotropic (homeotropic) tex-
tine samples PBSAN-6 to PBSAN-12, PBSAN-14 and PBSAN-16 undergo ture, respectively comprising linear birefringent defects (Fig. 2b) and
an endothermic phase transition from solid to mesomorphic state, flower-like texture/spherulitic domains (Fig. 2c). However, some of

3
M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

Scheme 1.

the phasmids displayed uniform (dark) domain of homeotropically DSC profiles of the LCs corroborate the inference described above of
aligned Colh phase where column axes are vertical to the glass surface; the POM study.
this is notable given the fact that the homeotropic alignment of The indication from the POM textural investigations that the newly
Col phase can be used in solar cells or OLEDs. Needless to say, the prepared phasmidic LCs exhibit a columnar hexagonal phase was sub-
large homeotropic domains appearing dark under POM reveal that stantiated with variable-temperature powder X-ray diffraction (XRD)
these LC phases are optically uniaxial, which is typical for the Colh experiments. XRD patterns were obtained for three compounds viz.,
phase. Thus, the Col phase formed by these compounds remains PBSAN-11, PBSAN-12, and PBSAN-14 as representative cases. The sam-
unaltered nearly up to room temperature (RT), and eventually, it trans- ples were heated to their isotropic liquid state and filled into capillary
forms into a solid-state with an exception for the member PBSAN-9 tubes (1 mm) of Lindemann glass. They were cooled into the Col
where the Col phase freezes (Table 1 & Fig. S21). The phase transitions phase at a rate of 5 °C / min, and the diffraction patterns of the LC
and the corresponding temperatures were found to be highly reproduc- phase were recorded at two different temperatures for each selected
ible for any number of heating/cooling scans during POM study, imply- sample. Figs. 4a, S22 & 4b respectively portray the 1D intensity vs dif-
ing that the synthesized phasmids possess excellent thermal stability fraction angle (2θ) profiles of mesogens PBSAN-11, PBSAN-12, and
and hydrolytic resistance. Fig. 3a and b depict the representative DSC PBSAN-14. Table 2 provides the Bragg reflections along with the results
traces obtained respectively for PBSAN-9 and PBSAN-14 where the pertaining to the detailed indexation of the mesophases of each
peak positions of the Col-I/I-Col phase transitions of the two consecutive phasmid LC. It is thus evident from the XRD patterns (Figs. 4a-b &
heating-cooling scans remain almost unaffected. Thus, as envisaged, S22) and the corresponding data collected in Table 2 that compounds

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M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

Table 1 diffractograms of the Col phase is characterized by the halo scattering

Phase transition temperatures (°C)a and associated enthalpies (kJ/mol) of transitions ob- corresponding to spacing (d) in the range of 4.3–4.56 Å, which stems
tained for the phasmidic mesogens of PBSAN–n series, Cr: Crystal; Colh/p6mm: Hexagonal
columnar phase having p6mm symmetry; I: isotropic liquid state.
due to the slow mobility of the molten n-alkoxy tails located on either
side of the central five-ring aromatic rigid core. The Col phase of
LCs Phase sequence phasmidic LCs may as well display a relatively sharp scattering in the
Heating; Cooling high-angle region (at Bragg angles 2θ ~ 25 deg) due to an intermolecular
PBSAN-5 Cr 151.7 (41.9) I; I 114 (1.27) Cr co-facial π-π interaction between the constituent mesogenic cores of a
PBSAN-6 Cr 112.9 (3.1) Colh/p6mm 118.9 (1.6) I; I 114.5 (1.5) Colh/p6mm 61.8 column. The lack of such an intracolumnar reflection, precisely the sig-
(3.18) Cr nature due to core-core separation, in the XRD profiles implies the like-
PBSAN-7 Cr 61.8 (3.9) Colh /p6mm 120 (1.6) I; I 116.4 (1.5) Colh/p6mm 44.0 lihood of disordered arrangement of the hexacatenar molecules within
(0.2) Cr
PBSAN-8 Cr 55.8 (5.5) Colh/p6mm 128.9 (2.2) I; I 125.2 (2.17) Colh/p6mm 39.5
the columnar structure of samples under discussion. The low angle re-
(0.7) Cr gion (0 < 2θ < 5 o) of all the diffraction scans comprises a strong reflec-
PBSAN-9 Cr 51.9 (2.4) Colh/p6mm 133.6 (2.3) I; I 128.8 (2.17) Colh/p6mm b tion along with three weak peaks (Fig. 4a; Table 2).
PBSAN-10 Cr 49.1 (2.4) Colh/p6mm 133.3 (2.2) I; I 130.18 (2.18) Colh/p6mm 61.8 It is known that all interplanar spacing distances, and thus, the re-
(0.3) Cr
flection peaks seen in the diffractograms will be in archetypal ratio
PBSAN-11 Cr 112.3 (4.4) Colh/p6mm 119.5 (2) I; I 115.1 (1.9) Colh/p6mm 62.3
(4.5) Cr values with reference to the first indexed peak. Thus, the spacings of
PBSAN-12 Cr 51.6 (8.9) Colh/p6mm 130.2 (1.8) I; I 125.4 (1.6) Colh/p6mm 53.1 these reflections were found to be in the ratio of 1:1/√3:1/√4:1/√7,
(1.0) Cr which could be indexed to (100), (110), (200), and (210) reflections
PBSAN-14 Cr 82.9 (9.7) Colh/p6mm 127.8 (2.4) I; I 125.6 (2.2) Colh /p6mm 23.5 of a quasi 2D hexagonal lattice. Thus, the investigated compounds
(19.2) Cr
PBSAN-16 Cr 51.6 (62.0) Colh/p6mm 120.2 (1.0) I; I 117.5 (0.9) Colh/p6mm 24.4
show a columnar phase featuring hexagonal 2D lattice. It may be
(3.6) Cr recalled here that the Colh phase formed by phasmidic LCs has the
a same symmetry as that of the discotic LCs. As is generally known, the
Transition temperatures determined by both polarizing optical microscope (POM) and
peak values of the DSC thermograms during the first heating/cooling cycles at 5 °C /min indexing of a Colh phase, belonging to the D6h point group symmetry,
rate. b The mesophase freezes at about 65 °C which remains unchanged upto - 60 °C (limi- is comparatively straightforward because of the high symmetry of the
tation of the instrument). p6mm plane group, which is equivalent to the p6/mmm space group. Ac-
cordingly, the Colh phase exhibited by the present PBSAN series of com-
pounds can be assigned with p6mm symmetry. The lattice parameter
PBSAN-11, PBSAN-12 and PBSAN-14 display an identical Col phase re- (a) determined for the Colh phase at the chosen temperatures of the
gardless of variations in their terminal chain length or the measurement mesogens has been collected in Table 2. As envisaged, the value of ‘a’ in-
temperatures. The high-angle area (for 2θ > ca 12-15o) of all the creases with the elongation of long terminal tails, meaning yet again

Fig. 2. POM images of the thin-films of Colh phase realized by cooling the representative samples from their isotropic phase contained between two untreated glass substrates: (a) The
pseudo focal-conic fan-like (planar) texture of PBSAN-10 (at 90 °C), (b) the pseudo isotropic (homeotropic) pattern accompanied by linear birefringent defects seen for PBSAN-11 at
110 °C and (c) the spherulitic /fan-shaped birefringent pattern along with the homeotropic texture shown by PBSAN-14 at 105 °C.

Fig. 3. DSC traces recorded for the two successive heating (h1,h2)-cooling (c1, c2) cycles at a rate of 5 °C for (a) PBSAN-9 and (b) PBSAN-14. Note that the peak positions of all the traces
match implying that the PBSAN LCs are heat and moisture resistant. Notice that compound PBSAN-14 crystallizes during the second heating cycle.

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M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

Fig. 4. 1D intensity vs 2θ profiles obtained for the Colh /p6mm phase of compounds PBSAN-11at 90 °C & 110 °C (a), and PBSAN-14 at 80 °C & 105 °C (b). Front view of a slice (disk-like
columnar core) resulting from the spontaneous self-assembly of a pair of phasmidic mesogens in a side-by-side fashion via π-π interaction (c). Schematic diagram of the Colh/p6mm
phase where the directionally correlated tilting of the slices within the columns is non-existent (d).

that the fundamental Col structure of all the compounds studied here is in the wide-angle area of XRD profile, was calculated from the experi-
indistinguishable. mental value of the unit cell parameter (a) and assuming a density of
However, the Colh phase of hexacatenars differs from that of the con- ρ = 1 g cm−3. According to the standard expression Z = (√3 a2 hNA
ventional discotic LCs in comparison to the molecular arrangements ρ)/2Mw, where MW is the molecular weight and NA is Avogadro's num-
within the columns. About two to several phasmidic molecules, driven ber, about 2.1 to 2.7 phasmidic mesogens constitute each slice of the col-
by the secondary forces (viz., H-bonding, π-π interaction, van der umns. That is, on an average, 2 to 3 molecules arranged in a side-by-side
Waals correlation, etc.), self-assemble in a side-by-side manner to manner via π-π interaction yield a disk-like columnar core (slice) where
yield a slice (molecular disk/core or disk-like stratum), and the slices the self-assembled five-ring aromatic cores act as central rigid structure
thus generated stack on top of one another to yield indefinitely long col- (hard region) and the peripheral tails not only fill the space but also
umns constituting a hexagonal 2D lattice. Precisely, the well-extended serve as the fluid (soft) region of the disk (Fig. 4c). Thus, the attractive
columns are shaped or filled with slices comprising a minimum of two π-π interactions coupled with nanophase segregation among the in-
phasmidic mesogens (Fig. 4c). However, the slices may have either up- compatible rigid and flexible domains of the molecules drive the forma-
right or tilted orientation with respect to the columnar axis in the LC tion of hexagonal columnar structure (Fig. 4d). It is important to discuss
phase. In order to figure out these aspects, the XRD results of the Colh the correlation between the columnar structure and the optical textures
phase along along with the molecular mass (M) values of the materials observed under the POM. As mentioned above, the pairs of molecules
were used. As can be seen in Table 2, the intercolumnar distance, the lat- (slices) tilt within the columns, and the average tilt angle is expected
tice parameter (a) derived, is notably smaller than the diameter (molec- to be nearly the same in different columns. This directionally correlated
ular dimension) of the fully stretched all-trans conformation of the tilting obviously reduces the symmetry of the macroscopic structure,
hexacatenars. With the literature survey results on this subject in meaning that the mesophase should be optically biaxial and thus, the
hand, this feature can be obviously attributed to the tilting of slices occurrence of homeotropic texture is ruled out. However, on the con-
with respect to the cross section of each column. The tilt angle (θ) of trary, the Colh phase formed by the PBSANs show homeotropic patterns
the 2D slice with respect to the normal to the columnar axis (i.e. along predominantly, implying that the directionally correlated tilting among
the longitudinal slice direction) was estimated using an expression the columns does not exist. That is, the tilt direction of the slices within
θ = 90-cos−1(a/L) where a and L respectively being the lattice parame- the columns is not correlated (Fig. 4c), and thus, the homeotropic tex-
ter and length of the mesogens in their most extended geometrical form ture is seen.
with an all-trans conformation of the alkoxy chains. Accordingly, the
measured tilt angles of the stacked molecules in the Col phase are: 37o 2.3. Photophysical studies
for PBSAN-11 and 42o for both PBSAN-12 and PBSAN-14.
The average number of molecules (Z) constituting a slice of the col- ESIPT is an exceptional four-level photochemical (E-E*-K*-K) pro-
umns with a height of h = ~ 4.5 Å, which is the broad diffuse maximum cess wherein the photoexcited molecules relax their energy via

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M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

Table 2
The results of (hkl) indexation of XRD profiles recorded at the specified temperature (T) of the columnar hexagonal phase of representative phasmidic LCs viz., PBSAN-11, PBSAN-12 and
PBSAN-14.

Compound (L/Å) Phase (T/°C) dobs (Å) dcal (Å) Miller indices hkl a: Lattice parameter (Å)
S: Lattice area (Å2)
V: Molecular volume (Å3)
Z: Number of molecules per column slice

PBSAN-11 (55.1) Colh 33.21 33.20 100 a = 38.34

90 19.17 19.17 110 S = 1273.01
16.57 16.60 200 V = 5690.39
12.55 11.67 210 Z = 2.17
4.47
Colh 33.31 33.30 100 a = 38.46
110 19.25 19.23 110 S = 1281
16.62 16.65 200 V = 5713.26
12.70 11.70 210 Z = 2.18
4.46
PBSAN-12 (56.6) Colh 37.94 37.93 100 a = 43.80
80 21.87 21.90 110 S = 1661.41
19.02 18.96 200 V = 7210.55
14.46 14.33 210 Z = 2.53
4.34
Colh 37.93 37.92 100 a = 43.79
100 22.21 21.89 110 S = 1660.6
18.92 18.96 200 V = 7290.21
14.42 14.33 210 Z = 2.51
4.39
PBSAN-14 (57.8) Colh 41.03 41.02 100 a = 47.37
80 24.79 23.68 110 S = 1943.20
20.56 20.51 200 V = 8647.63
15.60 15.52 210 Z = 2.70
4.45
Colh 41.10 41.09 100 a = 47.45
105 24.20 23.72 110 S = 1949.85
20.61 20.54 200 V = 8891.35
15.61 15.53 210 Z = 2.73
4.56

L = Length of the polycatenar mesogen estimated in its all-trans conformation from Chem 3D Pro 8.0 (Molecular model software from Cambridge Soft). dobs: Spacing observed; dcal: spac-
ing calculated (deduced from the lattice parameter ‘a’ for the Colh phase).

tautomerization from Enol (E)-form to Keto (K)-form essentially involv- room temperature. The temperature-dependent photoluminescence
ing intramolecular proton-transfer (PT) process. [73–82] As illustrated spectra for the Colh/p6mm phase were recorded for two representative
in Fig. 5, PBSAN molecules, being ESIPT fluorophores, stay in thermody- samples; in this mode, the emission spectra were also recorded in the
namically favored enol-imine (OH) tautomeric form at the ground (E, isotropic liquid state and solid/frozen Col phase of the samples. Given
S0) state due to the presence of H-bridged, the quasi six-membered the fact that all the members of the series vary structurally only with re-
ring formed by the intramolecular H-bonding between the H-atom spect to the length of terminal tails, they are expected to display identi-
and N-atom of the hydroxy and imine groups respectively (Fig. 5). cal photophysical properties. Thus, all the hexacatenars exhibited
After light absorption, the singlet excited (S1, E*,) state of the enol- analogous UV–Vis and fluorescence spectra. As shown in Fig. 6a, the
form, due to photoexcitation, gets populated but without the relaxation DCM solutions of the mesogens exhibit two distinct absorption maxima
of the geometry, which is in accordance with the Franck–Condon prin- viz., a strong band at ~360 nm and a weak peak at ~270 nm (Table 3)
ciple. The excited enolic state (E*), which may experience a radioactive possibly arising due to the π-π* and n-π* transitions respectively.
decay (emission) and revert to the original enolic form (E), necessarily Given the fact that the hexacatenars are characterized by the strong in-
undergoes ESIPT process much ahead of fluorescence, on a time scale tramolecular H-bonding, the aforesaid UV–Vis bands arising due to ag-
ranging from femtoseconds (fs) to picoseconds (ps), yielding the ex- gregation of the mesogens can be ruled out. As shown in Table 3, the
cited ketone species (K*, S1’). This means that ESIPT invariably occurs molar extinction coefficients (ε) determined for the higher wavelength
due to the keto tautomer. The excited ketone (K*) state decays to attain band were found to be in the range of 1.8 × 104 to 5.7 × 104 L mol−1 cm−1
ketone ground (K, S0`) state with the emission of light at lower energy (Table 3).
than the E* form; the large Stokes shift in fluorescence occurs due to Seemingly, the absorption bands fall in the UV region due to high ab-
the significant reorganization of the geometry. Subsequently, a reverse sorption coefficients implying that these materials readily absorb pho-
PT takes place to produce the fundamental enol-form. Thus, PBSAN tons. The corresponding emission spectra recorded for the excitation
mesogens should display dual emission – the first (normal) one at wavelength of 365 nm showed an intense peak at ~610 nm with a
lower wavelengths is due to enol-emission and second one at higher broad shoulder at ~660 nm; in addition, a weak absorbance band at
wavelengths with large Stokes shift resulting from the keto-tautomer ~430 nm exists in the spectra of some members of the series (Fig. 6b).
formed after PT (Fig. 5). It may be mentioned here that the colour of these solutions, appearing
Thus, to illustrate the aforesaid novel four-level photochemical yellow under daylight (Fig. 6b - left-inset and Fig. S23a), turns intense
phenomenon of the PBSANs realized in this study, photophysical orange when exposed to 365 nm light (Fig. 6b- right-inset and
measurements were carried out. UV–Vis electronic absorption and Fig. S23b). The strong band located at around 610 nm can be attributed
emission spectra of the solid samples, in the form of drop-casted thin- to ESIPT emission, whereas the less intense, blue-shifted band occurring
films, and dilute solutions of the compounds in dichloromethane at ~430 nm can be ascribed to the normal emission. It is immediately ap-
(DCM) (c = 1 × 10−4 mol L−1) using quartz cells were recorded at parent from the data collected in Table 3 that the Stokes shift is in the

7
M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

Fig. 5. Schematic representation of the ESIPT (four-level photochemical) process proposed for the PBSAN materials studied in this work.

range of 250–256 nm; this is important given the fact that the large The dependence of fluorescence intensity on the concentration was
Stokes shift prevents the self-absorption of the dyes or the inner filter probed for a representative material. The emission spectra recorded, for
effect. Such a large Stokes shift observed here for the ESIPT chromo- the excitation wavelength of 365 nm light, at the different con-
phores can be attributed not only to the geometry relaxation but also centrations of PBSAN-12 in DCM revealed that the fluorescence inten-
to the drastic change in geometry of the keto-form when compared to sity indeed increases with the increase in the concentration of the
that of the enol-tautomer. It may be worth mentioning here that the solute (Fig. S25a), as expected. Fig. S25b shows that the intensity of
fluorescence peak position and/or intensity appears to depend on the ESIPT (keto) fluorescence intensity when compared to that of the
polarity of the solvent used, which is shown in Fig.S24. normal (enol) one, increases progressively with an increase in the

Fig. 6. UV–Vis absorption (a) and photoluminescence spectra (b) of PBSAN-n series of mesogens at c = 1 × 10−4 mol L−1 in DCM. Insets of (b) are the photographs of the solution of
PBSAN-8 in DCM under daylight (left) and that exposed to UV light at 365 nm (right).

8
M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

Table 3
Photophysical data derived from the UV–Vis and photoluminescence spectra of PBSAN-n series of LCs recorded for their dilute DCM solutions and the solid (thin-film) states.

LCs Solution Stoke Extinction coefficient Solid (Thin-film) d Stoke

shiftc (L/mol.cm) shiftc
Absorptiona Emission a,b Absorptiond Emission b
[λabs, (nm)] [λem, (nm)] [λabs, (nm)] [λem, (nm)]

PBSAN-5 280,363 614 251 5.08 × 104 275, 354 629 275
PBSAN-6 265, 360 614 254 2.43 × 104 273, 353 629 276
PBSAN-7 286, 359 615 256 2.95 × 104 276, 359 628 269
PBSAN-8 278, 362 614 252 5.40 × 104 278, 356 629+ 273
PBSAN-9 280, 364 614 250 5.77 × 104 278, 360 626+ 266
PBSAN-10 281, 364 614* 250 4.59 × 104 278, 355 626+ 271
PBSAN-11 279, 364 614* 250 5.46 × 104 273, 353 625 272
PBSAN-12 286, 361 615* 254 3.14 × 104 278, 360 624+ 264
PBSAN-14 267, 360 615* 255 1.84 × 104 277, 357 625+ 268
PBSAN-16 279, 364 614* 250 3.83 × 104 278, 361 629 268
⁎A less intense, broad band exists at 430 nm (see Fig. 6b).
+
A less intense but broad peak occurs at 435 nm (see Fig. 7b).
a
Absorption and fluorescence spectra were obtained for the DCM solution of the samples. b The excitation wavelength was set at 360 nm. c Stoke shift = Difference between the position
of the peak maxima of the absorption band and the maximum of the fluorescence emission. d Drop-casted thin-films were made by placing dilute DCM solution of the samples on a
quartz plate.

concentration of the dye. The band maximum of the emission peak as be interesting. [76] Thus, the three condensed states viz., solid, Col LC
well as fluorescence (photoluminescence) quantum yield (ΦFL) of the phase, and isotropic liquid state of synthesized materials were probed
keto-tautomer fluorescence band, unlike that of the normal band, de- for their ESIPT fluorescence competence. The solid samples drop-
pend on several vital parameters, including the surrounding medium casted, using their DCM solutions, onto quartz substrate affording the
(environment). Thus, relative ΦFL of compound PBSAN-12, as a repre- thin-films were used to collect both UV − Visible and
sentative case, was measured by the comparative method where Nile photoluminescence spectra. Fig. 7a and b respectively portray the ab-
red dissolved in DMSO was used as an internal standard (Fig. S26). sorption and emission spectra of the thin-films of mesogens. The thin-
The expression employed for the calculation of ΦFL along with the rele- film pictures of PBSAN-12 as seen in the daylight and after exposure
vant details, has been given in SI. The quantum efficiency of this to UV light (365 nm) are shown as insets in Fig. 7b. UV–Vis spectra of
mesogenic dye for the longer emission was determined to be 0.12. the films possess two distinct absorption maxima, one being weak in
These results are in complete agreement with the fact that emission the range of 273–278 nm and another strong band in the range of
from the ESIPT state is characterized by a large Stokes' shift that enables 353–361 nm. These longer and shorter wavelength bands of the sam-
longer wavelength fluorescence by UV excitation and has the tendency ples possibly arise due to n-π* and the π-π* transitions, respectively.
to possess low ΦFL because of non-radiative deactivation events taking The photoluminescence spectra recorded for an excitation wave-
place at the keto-form excited (K*) state. [76] length of 360 nm, the wavelength of maximum absorbance of the
The majority of the organic fluorophores fluoresce highly in their di- thin-films, are presented in Fig. 7b. Apparently, some of the thin-films
lute solution with high fluorescence quantum efficiencies. However, the possess two emission bands at ~435 nm (weak) and ~ 625 nm (strong)
emissive behavior in their two condensed states viz., solid-state and liq- arising due to intramolecular proton transfer process via an excited
uid phase is generally feeble, and even remains absent, owing to the state. The occurrence of a strong longer wavelength fluorescence band
aggregation-caused quenching (ACQ) process; this is also applicable to in all the films with large Stokes shift (266 to 276 nm) suggests that
another condensed state, namely LC state of the mesogenic dyes. In ESIPT process takes over the relaxation of the excited enolic (E*) state
order to circumvent the ACQ concern, a number of strategies have to the original enolic form (E). The temperature-dependent
been explored to contain the other radiationless deactivation processes photoluminescence measurements on the fluid / frozen Col LC phase
occurring at the excited state; of these, aggregation-induced emission along with the isotropic liquid state were performed for the two repre-
(AIE) and aggregation-induced enhanced emission (AIEE) appear to sentative materials namely, PBSAN-9 and PBSAN-12; their respective

Fig. 7. The electronic absorption and photoluminescent spectra (a and b) of the drop-casted thin-films of the PBSAN-n series of compounds. The thin-film pictures of PBSAN-12 as seen
before, inset of (b)-top, and after the illumination with UV light (365 nm), inset of (b)-bottom.

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M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

phase sequences and transition temperatures (in parenthesis, oC) noted to enol-form (E*-E), whereas the emission band at a longer wavelength,
during the cooling cycle are: I (128.8) Colh – freezes at about 65, and I existing around 630 nm, can be convincingly assigned to keto-tautomer
(125.4) Colh (53) Cr. The samples held between quartz plates in minute (K*-K).
quantities were slowly heated to 150 °C (well above their isotropization As mentioned earlier, whereas the pattern of the
temperature) using a programmable hot stage where the top quartz temperature-dependent fluorescence spectra of the samples remains
substrate of each cell was pressed hard to spread the sample evenly. indistinguishable, their ESIPT photoluminescence (K*-K) intensity in-
Fig. 8a and c respectively depict the fluorescence spectra recorded at creases gradually with the decrease in temperature; this also true for
varying temperatures for the samples (excited at 360 nm) PBSAN-9 the intensity of normal emission. However, as shown in Fig. 8b and d,
and PBSAN-12 at 10 °C interval while cooling them from 150 °C to 40 °C. the magnitude of ESIPT fluorescence intensity of the Col phase belong-
The spectral signatures of both samples in their liquid state (in the ing to both the mesogens, when compared to that of the normal (E*-
temperature range of 130 to 150 °C) and fluid/frozen Colh phase (50 E) fluorescence emission, depends remarkably on the temperature
to 120 °C), were found to be virtually similar, except for peak intensities, that can be attributed to the breaking of larger aggregates or thermally
displaying dual-fluorescence emission; indeed, the analogous spectral activated non-radiative transitions [65,83–87]. Interestingly, the emis-
pattern was seen for the solid-state (40 and 50 °C) of PBSAN-12 (Ta- sion maxima of the ESIPT fluorescence spectra, recorded while progres-
ble S1). The weak emission appearing around 465 nm could be ascribed sive cooling of the Col phase of the compounds PBSAN-9 and PBSAN-12,

Fig. 8. Fluorescence spectra recorded as a function of temperature in the Colh phase which includes isotropic liquid and solid states of compounds PBSAN-9 (a) and PBSAN-12 (c); notice
here that the spectral signatures are identical in all the three condensed states, i.e. liquid state, fluid/frozen Colh LC phase and solid state. The temperature-dependence of the magnitude of
ESIPT fluorescence emission intensity and the normal (E*-E) fluorescence intensity of PBSAN-9 (b) and PBSAN-12 (d). The bathocromic shift of ESIPT fluorescence emission maxima
observed while cooling PBSAN-9 (e) and PBSAN-12 (f) from 150 °C to 40 °C implying J-aggregation.

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M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

seem to shift marginally, by and large, towards red (longer wavelength) LUMO for the enol-imine (E)/(OH) and keto-enamine (K)/(NH) states
end of the spectrum (Fig. 8e and f). of a representative material PBSAN-12, were obtained by the Hartree
This demonstration of narrow bathocromic shift of the emission Fock (HF) and Density-functional theory (DFT)-based calculations. The
maxima upon decreasing the temperature without photoluminescence HF calculations were performed using RHF single point energy func-
quenching of the Col phase (formed by the self-assembly of mesogens in tional and DFT calculations using B3LYP functional in conjunction with
the manner mentioned above) imply the formation of so-called Scheibe the def2-TZVP basis set in ORCA 4.01 software [95]. The optimized
or J-aggregates [88–90] where the π-π stacked aromatic cores within structures along with the HOMO and LUMO electron distribution and
the columns, oriented in a head-to-tail manner, tilt with respect to the the energy values/levels obtained from these (DFT and HF) studies
column axis of the column (Fig. 4c); this behavior completely agrees have been depicted in Fig. 9 (also see Figs. S27 and S28), and the rele-
with the Col LCs reported earlier. [65,91,92] The occurrence of vant data are collected in Table 4. The optimized structures of both
J-aggregates can be figured out by determining the tilted angle between enol and keto states (Fig. S28), the former being thermodynamically
the molecular plane and the aggregation (packing) direction. As per stable than the latter, reveal the coplanar conformation between hy-
the exciton-coupling theory [93,94], in the J-aggregates, wherein the droxyl and imine/keto and enamine groups that can be ascribed to
dipoles maintain a head-to-tail orientation of the constituent fluorop- the presence of strong intramolecular H-bonding, which accounts for
hores, and the tilted angle should be less than 54.7 degrees. The results the stability of different tautomeric forms of mesogens. That is, the in-
of X-ray diffraction analysis revealed that the tilted stacking angle mea- tramolecularly H-bonded cis-enol and cis-keto forms exist in the opti-
sured for PBSAN-12 is less than the aforesaid theoretical value viz. 42 mized structures.
degrees. This means that the phasmidic fluorophores spontaneously Apparently, the band gaps and electron densities are different for
self-assemble, through the strong π-π interactions (but not through in- enol and keto forms. According to the data presented in Table 4
termolecular H-bonding), into indefinitely long J-aggregates (columns), (Fig. 9), the HOMO energy level of keto-enamine form is higher than
which in turn arrange on a 2D hexagonal lattice (Fig. 4d). that of the enol state. In the enol-imine (OH) form, the HOMO orbitals
To corroborate the aforementioned photophysical results, the struc- are evenly localized on the central three benzene-rings whereas the
tural and energy parameters viz., electron distribution and band-gaps LUMO orbitals are delocalized mostly on the central benzene-ring
(energy levels) of the HOMO (highest occupied molecular orbital) and where both hydroxyl and imine groups are located; it is especially

Fig. 9. Theoretical parameters of ESIPT active mesogen PBSAN-12 (a representative case) derived from the DFT calculations: The optimized conformation structures, electron density
distributions in the HOMO and LUMO states of enol-imine (OH)/(E) and keto-enamine (NH)/(K) forms, and HOMO-LUMO energy levels (band-gaps).

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M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

Table 4 Table 5
Theoretically calculated HOMO−LUMO energy levels and band gap values derived from Electrochemical properties a of representative compounds.
both theory and experimental measurements.
Mesogens Eboxd EHOMO (eV) Ebred ELUMO (eV) ΔEcg.CV (eV) Edg.opt (eV)
Parameters of PBSAN-12 Enol-Imine (OH) Keto-Enamine (NH)
PBSAN -9 1.04 −5.84 −0.18 −4.62 1.22 2.40
form state
PBSAN - 11 0.96 −5.76 −0.20 −4.59 1.17 2.54
HF DFT HF DFT PBSAN - 16 1.00 −5.80 −0.17 −4.63 1.17 2.53
a
HOMO (eV) −7.8 −5.6 −6.9 −4.4 Experimental conditions: Room temperature measurements with a scanning rate of
LUMO (eV) 1.0 −2.3 0.9 −2.4 0.5 mVs−1; Ag/AgCl reference electrode, Pt-rod working electrode, Pt-wire counter elec-
ΔE (eV) 6.8 3.3 6.0 2.0 trode and TBAPF6 (0.1 M) in HPLC grade acetonitrile as a supporting electrolyte.
b
ΔE (eV) (Experimental) 3.3 (~ 376 nm) 2.0 (~ 621) Estimated from the onset oxidation and reduction potential (vs Ag/Ag+) plus 4.8.
c
Electrochemical band gaps were calculated from EHOMO and ELUMO.
d
Optical band-gaps were determined from the red edge of the longest wavelength
from the UV–Vis absorption of mesogens.
visible that in the LUMO state the electronic density at the nitrogen
atoms relatively more and thus they act as proton acceptor implying
that, the proton transfer is favored after the absorption of photons. It bandgap value viz.,3.3 eV derived from theoretical calculations for
is clear from the Fig. 9 that, in the keto-state, the HOMO is concentrated their homolog PBSAN-11. Therefore, one can assume that these
on three benzene-rings and the LUMO is localized on the keto and en- mesogens may have bandgap of about 3.0 eV and thus, they can be
amine groups. The HOMO-LUMO energy gaps derived from the DFT cal- regarded as wide-bandgap semiconducting columnar LC materials hav-
culations for enol and keto states are 3.3 eV (376 nm) and 2.0 eV ing the electronic characteristics falling between those of conventional
(621 nm), respectively; the corresponding experimentally measured semiconductors and insulators. This hypothesis is also supported by
values were found to be 2.8 eV (430 nm) and 2.0 eV (621 nm). Seem- the fact that the electronic absorption and ESIPT phenomenon of these
ingly, the theoretical and experimental HOMO-LUMO band gap values novel mesogens respectively take place in the near-ultraviolet and visi-
of the keto-form are in good agreement with each other. Overall, this ble spectral ranges.
theoretical study undertaken here clearly substantiates the experimen- As described earlier, in the ESIPT phenomenon, the photoexcited
tally observed photo-excitation induced ESIPT occurring in the mesogens relax their energy by converting themselves from enol-state
phasmidic LCs synthesized. to keto-form wherein intramolecular PT occurs. Thus, the presence of
hydroxyl (-OH) group enabling intramolecular PT is essential for the
ESIPT process to happen. This means that the ESIPT activity is basically
2.4. Electrochemical properties governed by the electronic environment of both imine (proton
acceptor) and oxygen atom of the hydroxyl group (proton donor) of
The cyclic voltammetry (CV) technique was employed to study the the cis-enol tautomer. Needless to say, by varying the electron density
reduction and oxidation characteristics of the ESIPT active mesogens at the nitrogen (acceptor) atom and/or oxygen (donor) atom, the pro-
synthesized. As representative cases, PBSAN-9, PBSAN-11, and ton transfer process leading to dual emission property of ESIPT active
PBSAN-16 were examined for their redox behavior by using a conven- molecules can be modulated. One of the well-known methods of
tional three-electrode cell comprising a set of working electrode, coun- accomplishing this task is to treat such fluorophores with metals
ter electrode, and reference electrode. While the reference electrode forming cations (metal-ions). From another standpoint, one can say
determines the applied potential, the current flows between the coun- that with the help of such binding studies, the occurrence of ESIPT pro-
ter and working electrodes. Precisely, Ag/AgCl (reference electrode), cess in functional materials can be evidenced with great ease. Hence, the
platinum rod (working electrode), and platinum wire (counter phasmidic LCs, having two binding (chelating) sites, each consisting of a
electrode) were employed. TBAPF6 (tetrabutylammonium hexaflu- hydroxyl group and an imine unit, were screened for their binding abil-
orophosphate, 0.1 M) in acetonitrile (HPLC grade) was used as a ities in solutions with different metal ions such as Cr6+, Mn2+, Hg2+,
supporting electrolyte. The room temperature measurements were Au3+, Zn2+, Cu2+, Ni2+and Fe3+. The binding (chelating) ability of a
conducted at a scanning rate of 0.5 mVs−1. Ferrocene /ferrocenium representative ligand PBSAN-16 for the aforesaid metal ions was tested
ion (Fc/Fc+) couple was employed as the internal reference, and all by monitoring changes in light emission properties. The titrated solu-
the potentials were calibrated with the same system; here, it assumed tions, obtained after the drop-wise addition of metal salt (CrO3, MnCl2,
that the energy level of the Fc/Fc + pair is 4.8 eV below the vacuum Hg(OAc)2, HAuCl4, Zn(OAc)2, Cu(OAc)2, NiCl2, FeCl3) solutions (50 μL)
level. The samples used for analysis were the same as those for UV– in DMF (c = 0.5 M) to the 10 mL of PBSAN-16 in DCM (c = 10−4 M),
Vis experiments. As depicted in Fig. S29, all the mesogens functional were subjected to their photoluminescence behavior. The photographs
groups such as hydroxyl and imine segments in their molecular struc- obtained for the probe PBSAN-16 in DCM and those of the titrated solu-
ture. The energy levels of the HOMO and LUMO were determined tions under 365 nm light are shown in Fig. 10a and Fig. 10b, respec-
using the formulas EHOMO = −(4.8 + Eox,onset) eV and ELUMO = tively. The emission spectra recorded for these titrated solutions,
−(4.8 + Ered,onset) eV. The electrochemical band-gap (ΔEg.CV) between excited at 365 nm, are shown in Fig. 11.
the frontier orbitals was determined using the expression ΔEg.CV =
EHOMO - ELUMO eV. The optical band gap (ΔEg.opt) values were figured
out from the longest wavelength absorption onset of the absorption
spectra of mesogens by using the expression E = 1240/λonset. The elec-
trochemical band gap values of these mesogens determined using their
voltammograms and absorption spectra are in the range of 1.17–1.22 eV
and 2.40–2.54 eV respectively (Table 5). The comparison reveals that
the electrochemical band gaps are lesser than those derived from the
optical method and such discrepancy can be ascribed to several factors
such as the electrode characteristics (size, surface, heterogeneity),
media (the status of electrolyte –oxygen content), pre-adsorbed gases,
molecular adsorption/desorption, double layer charging/discharging,
2D surface diffusion etc. However, it appears that the electrochemical Fig. 10. Photographs captured under a UV lamp (365 nm) for the mesogen PBSAN-16 in
band gaps of the compounds (ca 2.5 eV) are relatively closer to the DCM before (a) and after treating with the various metal salts in DMF (b).

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M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

Fig. 11. (a) Photoluminescence spectra recorded at room temperature for the solutions formed by treating the probe PBSAN-16 in DCM with different metal salts in DMF; (b) fluorescence
spectra of ligand PBSAN-16 in DCM (red-trace) and after treating with Zn2+ ions (green-trace) (Excitation wavelength is 360 nm).

The presence of Cr6+and Fe3+ ions alters drastically the HOMO and LUMO for the enol and keto states determined by HF and
photoluminescence profile of the ligand PBSAN-16 where the bands DFT-based calculations support the photophysical experimental obser-
due to dual fluorescence pertaining to the normal and ESIPT emissions vations. The evaluation of metal ions chelating property reveals that a
vanish completely (Fig. 11a) that can be ascribed to the collisional mesogen (as a representative case) selectively binds to certain metal
quenching coupled with the formation of coordination complexes. The ions to form metal complexes; notably, the complex formation of
complex formation especially disrupts ESIPT activity of the probe mole- mesogen with Zn2+ ions not only enhances the emission intensity but
cules. The addition of Cu2+ and Ni2+ also perturbs the emission prop- also shifts the peak towards shorter wavelength. The electrochemical
erty of the ligands to the extent that the ESIPT band (~ 600 nm) band gap values determined from the CV experiments appear to
remains absent that can be attributed yet again to the formation of com- match with those derived from the theoretical calculations closely. In
plexes; however, the existence of three emission bands at ca 410, 430 essence, these phasmidic columnar LCs exhibiting ESIPT phenomenon
and 460 nm, suggests that the coordination compounds generated are and other physicochemical properties may serve as functional materials
photoluminescent. More or less, no changes in the emission spectra for various technological applications.
were noticed when Mn2+, Hg2+ and Au3+ ions were treated with the
ligand, implying that these metal ions do not chemically interact with 4. Experimental
probe molecules. Interestingly, as shown in Fig. 11b, the interaction of
Zn2+ ions with PBSAN-16 molecules not only augments the fluores- 4.1. IGeneral remarks
cence emission intensity but also shifts the ESIPT peak towards a shorter
wavelength (blue shift). In essence, these experiments clearly substan- 4.1.1. General information (materials and methods)
tiate the fact that the phasmidic molecules studied here not only are Gallicacid, n-alkylbromides, 4-nitrophenol and 1,2-dimethox-
ESIPT active but also can serve as chemosensors. ybenzene procured from Sigma-Aldrich Company were utilized as re-
ceived. Organic solvents employed for various general purposes were
3. Conclusion distilled prior to use. Silica gel thin layer chromatography (TLC) was
used to monitor the progress of the organic reactions and also assess
In this article, we have presented the synthesis, structural character- the purity of the compounds synthesized, especially the intermediates.
ization, mesomorphism, photophysical behavior, redox activity, metal In particular, TLC plates consisting of a thin layer of silica gel (Merck,
ion sensing ability and solvatochromism of ten new, ESIPT active, Kieselgel60, F254) on an aluminium foil backing were employed. The
phasmidic bis(N-salicylideneaniline) LCs belonging to a homologous se- column chromatography was performed using glass columns packed,
ries. They have been readily synthesized with notable yields by the acid- by the wet method, with either neutral alumina or silica gel (60–120/
catalyzed condensation of two moles of lipophilic (half-disk shaped) 100–200 mesh) as the solid support. UV–Vis spectra of the samples
amines with one mole of 2,3-dihydroxyterephthalaldehyde. These o- were recorded using Perkin–Elmer's Lambda 750, 2015 NIR spectropho-
hydroxy Schiff bases, being resistant to heat and moisture, which can tometer. FTIR spectra of the samples were obtained from Perkin-Elmer
be attributed due to the presence of hydrogen (H)-bridged quasi six- Spectrum 1000 FT-IR spectrometer, and the typical unit used in the
membered rings, display columnar LC phase. The optical textural pat- spectra is wave numbers (which is cm−1). Fluorescence emission
terns combined with XRD data analysis confirm the presence of Colh (photoluminescence) spectra of all the ESIPT active molecules synthe-
having p6mm symmetry. XRD results imply that the slices (disk-like co- sized were collected, in their solid, solution amd LC phases, using a spec-
lumnar core), formed by the self-assembly of two molecules in a side- trofluorometer Flurolog-3, Horiba Jobin Yvon. Nuclear magnetic
to-side fashion, tilt with respect to the columnar axis and tilt direction resonance (NMR) spectra were recorded with the help of a Bruker
among the columns is not correlated; the profiles also show that the AMX-400 spectrometer operating at 400 MHz for 1H and 100 MHz for
13
core-core (slice-to-slice) interactions are too weak. Photophysical mea- C. The 1H NMR chemical shifts (δ) are presented in parts per million
surements clearly revealed the intrinsic ESIPT phenomenon not only in (ppm) relative to tetramethylsilane (TMS) peak (δ 0.0). The spectra
their dilute solutions but also in their solid, liquid crystal (Col) phase were obtained at room temperature from solutions of the samples dis-
and isotropic liquid state. In the Colh phase, the magnitude of ESIPT fluo- solved in deuterated chloroform (CDCl3) with residual solvent serving
rescence emission intensity display temperature-dependence; the as internal standard (7.26 ppm for 1H and 77.16 ppm for 13C). The
emission maxima shifts to longer wavelengths upon decreasing the data (the nature of the proton NMR peaks) are reported as s (singlet),
temperature confirming the J-type aggregation in the mesophase. Elec- d (doublet), t (triplet), and m (multiplet). The coupling constants
tron distribution in the optimized structures and band-gaps of the (J values), calculated directly from the spectra, are given in Hertz (Hz).

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M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

Integration has been determined as the relative number of atoms. An CDCl3): 13.45 (s, 2H, OH), 8.68 (s, 2H, CHN), 7.42 (d, 8H, J = 8 Hz, Ar),
elemental analyzer, namely, Elementar Vario MICRO Select, was 7.30 (d, 4H, J = 4 Hz, Ar), 7.03 (s, 2H, Ar), 4.07 (m, 12H, 6 × OCH2),
employed to determine the elemental compositions of the materials. 1.86 (m, 90H, 36 × CH2, 6 × CH3) 13C NMR (100 MHz): 165.13,
DFT calculations were performed with optimized structures using 162.23, 153.10, 150.59, 150.29, 145.79, 143.21, 123.72, 122.98, 122.38,
B3LYP functional in conjunction with the def2-TZVP basis set in ORCA 121.45, 120.71, 108.66, 77.36, 77.11, 76.85, 73.70, 69.37, 31.82, 31.64,
4.01 software. The calculations were mainly used to evaluate the elec- 30.38, 29.34, 25.84, 25.79, 22.77, 22.71, 14.12. Anal. calcd for
tronic structural properties of phasmidic mesogens in their cis-enol C82H120N2O12: C, 74.28; H, 9.12; N, 2.11; Found: C, 74.48; H, 9.54;
and cis-keto forms. The HF calculations were performed using RHF sin- N, 2.31.
gle point energy functional. PBSAN-9: A brown colour solid; yield: 0.125 g (72%); IR (KBr pellet):
The mesogenic materials synthesized were examined for their ther- νmax in cm−1 3442, 2921, 1734, 1618, 1585, 1186, 954, 857. UV - Vis:
mal / mesomorphic properties using an Olympus BX50 (Model BX50F4) λmax = 364 nm, ε = 5.77 × 104 L mol−1 cm−1; 1H NMR (400 MHz,
polarizing optical microscope (POM) equipped a digital camera and a CDCl3): 13.47 (s, 2H, OH), 8.68 (s, 2H, CHN), 7.42 (d, 8H, J = 8 Hz, Ar),
hot stage, Mettler FP82HT having FP90 central processor. Differential 7.30 (d, 4H, J = 8 Hz, Ar), 7.03 (s, 2H, Ar), 4.09 (m, 12H, 6 × OCH2),
scanning calorimeter (DSC) traces were registered at a scanning rate 1.87 (m, 102H, 42 × CH2, 6 × CH3) 13C NMR (100 MHz): 165.13,
of 5 °C/min using Perkin-Elmer DSC 8000 equipment. The calibration 162.23, 153.09, 150.59, 145.78, 143.21, 123.71, 122.98, 122.38, 121.45,
of the instrument prior to use was performed using pure indium as a 120.70, 108.66, 77.37, 77.11, 76.86, 73.70, 69.37, 31.99, 29.69, 29.50,
standard. Powder X-ray diffraction measurements were performed 29.39, 26.18, 22.78, 14.21. Anal. calcd for C88H132N2O12: C, 74.96;
with the help of either Panalytical (Empyrean) or Xenocs, Genix Cu H, 9.44; N, 1.99; Found: C, 75.27; H, 9.73; N, 2.27.
MAR345 using Cu-Kα (1.54 Å) radiation. The samples held in PBSAN-10: A brown colour solid; yield: 0.128 g (73%); IR (KBr pel-
Lindemann capillaries (0.5 mm diameter) and carefully flame sealed let): νmax in cm−1 3432, 2924, 1730, 1618, 1586, 1186, 959, 859. UV -
at both ends were employed. Vis: λmax = 368 nm, ε = 4.59 × 104 L mol−1 cm−1; 1H NMR
(400 MHz, CDCl3): 13.46 (s, 2H, OH), 8.68 (s, 2H, CHN), 7.42 (d, 8H,
4.2. General synthetic procedure for (((2,3-dihydroxy-1,4-phenylene) bis J = 8 Hz, Ar), 7.29 (d, 4H, J = 4 Hz, Ar), 7.03 (s, 2H, Ar), 4.07 (m, 12H,
(methanylylidene)) bis(azanylylidene)) bis(4,1-phenylene) bis(3,4,5-tris 6 × OCH2), 1.85 (m, 114H, 48 × CH2, 6 × CH3) 13C NMR (100 MHz):
(hexyloxy)benzoate)s (PBSAN-n series) 165.13, 162.23, 153.10, 150.58, 150.31, 145.80, 143.28, 123.72, 122.98,
122.38, 121.44, 120.70, 108.63, 77.11, 76.86, 73.70, 69.37, 31.99, 29.69,
A mixture of 2,3-dihydroxyterephthalaldehyde (7) (0.4 mmol,1 eq.) 29.38, 26.17, 22.77, 14.20. Anal. calcd for C94H144N2O12: C, 75.56;
and freshly purified 4-aminophenyl 3,4,5-tris(alkyloxy)benzoate H, 9.71; N, 1.87; Found: C, 75.93; H, 10.02; N, 2.03.
(0.8 mmol, 2 eq.), a catalytic amount of acetic acid in ethanol (10 mL) PBSAN-11: A brown colour solid; yield: 0.125 g (69%); IR (KBr pel-
was refluxed under an inert atmosphere for 2 h. The pale brown solid let): νmax in cm−1 3433, 2929, 1729, 1615, 1585, 1187, 961, 859. UV -
separated upon cooling the reaction mixture was collected by filtration, Vis: λmax = 364 nm, ε = 5.46 × 104 L mol−1 cm−1; 1H NMR
washed with ethanol, and dried. The crude product was purified by re- (400 MHz, CDCl3): 13.47 (s, 2H, OH), 8.68 (s, 2H, CHN), 7.42 (t, 8H,
peated recrystallizations in absolute ethanol (Yield: 69–75%). J = 4 Hz, Ar), 7.29 (d, 4H, J = 4 Hz, Ar), 7.03 (s, 2H, Ar), 4.09 (m, 12H,
PBSAN-5: A brown colour solid; yield: 0.125 g (70%); IR (KBr pellet): 6 × OCH2), 1.86 (m, 126H, 54 × CH2, 6 × CH3) 13C NMR (100 MHz):
νmax in cm−1 3434, 2955, 1729, 1615, 1585, 1188, 955, 863. UV - Vis: 165.13, 162.23, 153.09, 150.589150.29, 145.79, 143.21, 123.72, 122.98,
λmax = 363 nm, ε = 5.08 × 104 L mol−1 cm−1; 1H NMR (400 MHz, 122.38, 121.45, 120.71, 108.66, 77.36, 77.11, 76.85, 73.70, 69.37, 31.82,
CDCl3): 13.47 (s, 2H, OH), 8.68 (s, 2H, CHN), 7.42 (d, 8H, J = 8 Hz, Ar), 31.64, 30.38, 29.34, 25.84, 25.79, 22.77, 22.71, 14.18, 14.12. Anal. calcd
7.29 (d, 4H, J = 4 Hz, Ar), 7.03 (s, 2H, Ar), 4.09 (m, 12H, 6 × OCH2), for C100H156N2O12: C, 76.10; H, 9.96; N, 1.77; Found: C, 76.45;
1.87 (m, 54H, 18 × CH2, 6 × CH3) 13C NMR (100 MHz): 165.13, H, 10.34; N, 1.94.
162.23, 153.10, 150.58, 150.29, 145.78, 143.20, 123.73, 122.98, 122.39, PBSAN-12: A brown colour solid; yield: 0.110 g (70%); IR (KBr pel-
121.45, 120.71, 108.66, 77.37, 77.12, 76.86, 73.66, 69.36, 30.09, 29.06, let): νmax in cm−1 3433, 2920, 1735, 1619, 1586, 1237, 1186, 948, 855.
28.33, 28.27, 22.63, 22.52, 14.18, 14.13. Anal. calcd for C64H84N2O12: UV - Vis: λmax = 359 nm, ε = 3.41 × 104 L mol−1 cm−1; 1H NMR
C, 71.62; H, 7.89; N, 2.61; Found: C, 71.84; H, 8.03; N, 2.89. (400 MHz, CDCl3): 13.47 (s, 2H, OH), 8.68 (s, 2H, CHN), 7.42 (t, 8H,
PBSAN-6: A brown colour solid; yield: 0.100 g (72%); IR (KBr pellet): J = 4 Hz, Ar), 7.29 (d, 4H, J = 4 Hz, Ar), 7.03 (s, 2H, Ar), 4.08 (m, 12H,
νmax in cm−1 3435, 2930, 1729, 1619, 1587, 1183, 947, 866. UV - Vis: 6 × OCH2), 1.87 (m, 138H, 60 × CH2, 6 × CH3) 13C NMR (100 MHz):
λmax = 350 nm, ε = 2.43 × 104 L mol−1 cm−1; 1H NMR (400 MHz, 165.13, 162.23, 153.09, 150.59, 150.29, 145.79, 143.21, 123.71, 122.98,
CDCl3): 13.47 (s, 2H, OH), 8.68 (s, 2H, CHN), 7.42 (d, 8H, J = 8 Hz, Ar), 122.38, 121.45, 120.71, 108.66, 77.36, 77.11, 76.86, 73.70, 69.37, 32.02,
7.29 (d, 4H, J = 4 Hz, Ar), 7.03 (s, 2H, Ar), 4.08 (m, 12H, 6 × OCH2), 30.44, 29.80, 29.73, 29.49, 26.18, 22.79, 14.22. Anal. calcd for
1.86 (m, 66H, 24 × CH2, 6 × CH3) 13C NMR (100 MHz): 165.13, C106H168N2O12: C, 76.58; H, 10.19; N, 1.69; Found: C, 76.90; H, 10.54;
162.23, 153.08, 150.57, 150.28, 145.78, 143.18, 123.71, 122.98, 122.38, N, 1.83.
121.44, 120.70, 108.63, 77.34, 77.09, 76.84, 73.69, 69.36, 31.95, 30.43, PBSAN-14: A brown colour solid; yield: 0.128 g (75%); IR (KBr pel-
29.59, 29.38, 26.17, 22.77, 14.20. Anal. calcd forC70H96N2O12: C, 72.63; let): νmax in cm−1 3432, 2919, 1733, 1616, 1585, 1184, 949, 857. UV -
H, 8.36; N, 2.42; Found: C, 72.91; H, 8.66; N, 2.51. Vis: λmax = 360 nm, ε = 1.84 × 104 L mol−1 cm−1; 1H NMR
PBSAN-7: A brown colour solid; yield: 0.105 g (74%); IR (KBr pellet): (400 MHz, CDCl3): 13.47 (s, 2H, OH), 8.68 (s, 2H, CHN), 7.42 (t, 8H,
νmax in cm−1 3432, 2926, 1731, 1617, 1586, 1186, 936, 857. UV - Vis: J = 4 Hz, Ar), 7.29 (d, 4H, J = 4 Hz, Ar), 7.03 (s, 2H, Ar), 4.08 (m, 12H,
λmax = 356 nm, ε = 2.95 × 104 L mol−1 cm−1; 1H NMR (400 MHz, 6 × OCH2), 1.85 (m, 162H, 72 × CH2, 6 × CH3) 13C NMR (100 MHz):
CDCl3): 13.47 (s, 2H, OH), 8.68 (s, 2H, CHN), 7.42 (d, 8H, J = 8 Hz, Ar), 165.13, 162.23, 153.09, 150.59, 150.29, 145.79, 143.21, 123.70, 122.99,
7.29 (d, 4H, J = 4 Hz, Ar), 7.03 (s, 2H, Ar), 4.08 (m, 12H, 6 × OCH2), 122.38, 121.45, 120.71, 108.66, 77.36, 77.10, 76.85, 73.71, 69.37, 32.03,
1.86 (m, 66H, 30 × CH2, 6 × CH3) 13C NMR (100 MHz): 165.10, 30.44, 29.85, 29.81, 29.74, 29.49, 26.18, 22.79, 14.22. Anal. calcd for
162.21, 153.08, 150.59, 150.28, 145.79, 143.19, 122.97, 122.36, 121.40, C118H192N2O12: C, 77.41; H, 10.57; N, 1.53; Found: C, 77.94; H, 10.77;
120.66, 108.65, 77.36, 77.10, 76.82, 73.66, 69.34, 32.01, 31.87, 30.42, N, 1.93.
29.38, 29.12, 26.09, 22.69, 14.16. Anal. calcd for C76H108N2O12: PBSAN-16: A brown colour solid; yield: 0.105 g (71%); IR (KBr pel-
C, 73.51; H, 8.77; N, 2.26; Found: C, 73.88; H, 9.09; N, 2.47. let): νmax in cm−1 3435, 2919, 1731, 1618, 1587, 1187, 947, 866. UV -
PBSAN-8: A brown colour solid; yield: 0.120 g (71%); IR (KBr pellet): Vis: λmax = 364 nm, ε = 3.83 × 104 L mol−1 cm−1; 1H NMR
νmax in cm−1 3432, 2925, 1731, 1617, 1586, 1186, 950, 859. UV - Vis: (400 MHz, CDCl3): 13.47 (s, 2H, OH), 8.68 (s, 2H, CHN), 7.42 (t, 8H,
λmax = 362 nm, ε = 5.40 × 104 L mol−1 cm−1; 1H NMR (400 MHz, J = 4 Hz, Ar), 7.29 (d, 4H, J = 4 Hz, Ar), 7.03 (s, 2H, Ar), 4.08 (m, 12H,

14
M.B. Kanakala and C.V. Yelamaggad Journal of Molecular Liquids 332 (2021) 115879

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