Journal of Molecular Liquids 346 (2022) 117879

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Journal of Molecular Liquids

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

Rodlike 4,6-diamino-1,3,5-triazine derivatives, effect of the core length

on mesophase behavior and their application as LE-LCD device
Xiaoping Tan a,b, Qing Chang a, Fawu Su a, Yu Cao c,⇑, Feng Liu c, Xiaohong Cheng a,⇑
a
Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Research & Development Center for Natural Products, School of Chemical Science
and Technology, Yunnan University, Kunming 650091, PR China
b
College of Chemistry and Chemical Engineering, Yangtze Normal University, Fuling 408100, PR China
c
State Key Laboratory for Mechanical Behaviour of Materials, Shaanxi International Research Center for Soft Matter, Xi’an Jiaotong University, Xi’an 710049, PR China

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

Article history: Three series of diaminotriazine derivatives with different core length have been synthesized, and the
Received 29 July 2021 influence of the structural variation as well as the temperature on their mesophase behaviour were sys-


Revised 6 September 2021 tematically investigated. With focus on the formation of CubI/Im 3 m phase, multiple 2D/3D phases were
Accepted 16 October 2021
discovered. Confirmed by polarized optical microscope, small/wide angle X-ray scattering, grazing inci-
Available online 31 October 2021
dent small-angle X-ray scattering as well as molecular dynamics simulation, the results indicate that
molecular curvature


is critical to self-assembly structures. Moreover, the prerequisite for the formation
Keywords:
of the CubI/Im 3 m phase is intermediate molecular curvature on the surface of the micelle to allow the
Cubic phases
Diaminotriazine derivatives
intercalation of the alkyl chains. Finally, the potentials for such compounds as light-emitting liquid crys-
Photophysical properties tal display (LE-LCD) device has been initially demonstrated.
Liquid crystal display Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction
Rational design of nanostructure plays an essential role in
developing novel nanomaterials for industrial and technological
applications. Liquid crystal (LC) combining mobility and order on
molecular level supplies an effective way to realize 1D, 2D and
3D complex nanostrcutures in a controlled manner [1a-c]. Among
different LC mesophases, cubic phases which are divided into two
classes including bicontinuous cubic phases (CubV) and micellar
cubic phases (CubI) represent beautifully complex 3D nanostruc-
tures [1]. Complex thermotropic bicontinuous cubic phases (CubV)



such as Ia 3 d [2] and Pn 3 m [3] have been recently realized by
molecular rational design [4]. As micellar cubic phases (CubI)
which are resulted from the complex self-assembly of spherical/-


spheroidic supramolecular aggregates, Pm 3 n phase is the most

2. Experimental sections
common one in thermotropic liquid crystals, while Im 3 m phase
is the relatively rarely observed [5]. Whatever there missed a prin-
ciple about how to control the occurence of the defined quasicrys-
tals and cubic phase.
Moreover, light-emitting liquid crystal displays (LE-LCDs), serving
as emissive displays, are considered as promising alternatives to con-
⇑ Corresponding authors.
E-mail addresses: yu.cao@xjtu.edu.cn (Y. Cao), xhcheng@ynu.edu.cn (X. Cheng).
ventional LCDs because of their superior power efficiency [6]. Tri-
azine, generally, are known to be good electron conductors and
therefore have been used as electron transport layer in organic light
emitting diodes (OLEDs) [7]. However, relative to other conventional
heterocycles, their applications in LE-LCDs are rare. In order to estab-


lish the precise designing principle of Im 3 m phase and evaluate the
potential application of triazine LCs, herein we have investigated
three series of diaminotriazine derivatives with different core length,
namely the monothiophene series 1Tmn with one thiophene in the
rigid core, nonthiophene series 0T3n and bisthiophenene series
2T3n (Scheme 1). The influence of the structural variation as well
as the temperature on their mesophase behaviour were systemati-


cally investigated, focusing on the formation of CubI/Im 3 m phases.
2.1. Materials
4-methoxybenzene boronic acid, 2,5-dibromo-thiophene, 4-
hydroxybenzaldehyde, 2-bromothiophene, dicyandiamide, boron
tribromide, cuprous cyanide and so forth are purchased from
Shanghai Titan Scientific Co. Ltd. The synthetic route and NMR data
of diaminetriazine derivatives rTmn are provided in Supporting
Information (SI). Other chemical reagents are analytical grade.
The characterized instruments are described in SI.

https://doi.org/10.1016/j.molliq.2021.117879
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
X. Tan, Q. Chang, F. Su et al.
Scheme 1. Structures of the diaminotriazine derivatives rTmn under investigation
[For the notation of the compounds, r represents the number of thiophene (T), m
and n represent the number and length of alkyl chains connected to the non-polar
side of the molecule, respectively]. Monothiophene diaminotriazine derivatives
1Tmn with triple alkylchain (m = 3, n = 10,12,14,16) have been reported elsewhere
[8].
2.2. Mesomorphic property measurement
The liquid crystalline properties of these synthesized com-
pounds were investigated with polarizing optical microscopy
(POM, Optiphot 2, Nikon, in conjunction with a FP 82 HT heating
stage, Mettler), differential scanning calorimetry (DSC, NETZSH
200F 3) and synchrotron-based small-angle X-ray scattering
(SAXS).
2.3. Synthesis of the diaminotriazine derivatives rTmn
Scheme 2 shows the synthesis of the three series of target
derivatives rTmn. The Suzuki cross-coupling reaction of 2,5-
dibromothiophene with 4-methoxy phenyl boronic acid yielded
the single-coupling product 3. Kumada coupling reaction between
Scheme 2. Synthesis of the diaminotriazine derivatives; Reagents and conditions: i) Pd(PPh3)4, Na2CO3, toluene/H2O(1/1), 100 °C; ii) CuCN, DMF, 95 °C; iii) BBr3, CH2Cl2, 0 °C-
RT; iv) NaN3, TfOH, acetonitrile, RT; v) Mg, THF; vi) Ni(dppp)Cl2, THF, 20 °C; vii) NBS, THF, 20 °C; viii) K2CO3, DMF, 90 °C; iv) Dicyandiamide, 2-methoxyethanol, KOH.
2
Journal of Molecular Liquids 346 (2022) 117879
3 and Grignard reagent of 2-bromo-thiophene 9 yielded 11 which
was bromided with NBS, and then the compounds 4 and 13 were
obtained from compounds 3 and 12 by reaction with CuCN in
DMF [9], respectively. After cleavage of the methoxy group in com-
pounds 4 and 13 by BBr3, the yielded phenols 5 and 14 were fur-
ther etherified with the appropriate benzyl chloride 6, leading to
the corresponding cyanothiophene derivatives 15–17. Subsequent
reaction with dicyandiamide and KOH in 2-methoxyethanol gave
diaminotriazine derivatives 0T3n, 1Tmn and 2T3n respectively,
which were purified by column chromatography.
3. Results and discussion
3.1. Mesomorphic properties of nonthiophene 0T3n and bisthiophene
2T3n diamino triazine derivatives
Three triple chain nonthiophene diaminotriazine series 0T3n
(n = 12, 14, 16) with the shortest core length were synthesized.
All represented exclusively enantiotropic and optically isotropic


CubI/Pm 3 n phases (Table 1), which are highly viscous soft solids
observed under POM (Fig. S1). Take 0T316 for example, as the tem-
perature increases, obvious transition into isotropic liquid with
high mobility was observed at a given temperature, which can also
be observed as evident peaks in the DSC curves (Fig. S2c). The for-
mation of the isotropic mesophases can be supercooled as typical
characteristic of mesophase with 3D periodicity [10] (see insert


in Fig. S2c). The CubI/Pm 3 n phases of these compounds were fur-
ther confirmed by SAXS investigation (Fig. 1, Table 1). The location
of the sharp reflections in the small-angle region is consistent with


that of the cubic lattice with Pm 3 n space group (see Figs. 1, S3, S4,
Tables S1, S2, S3). The calculated lattice parameters are acub = 9.39,
9.58 and 9.67 nm for 0T312, 0T314 and 0T316 respectively. These
compounds show diffuse scattering in the wide-angle region, indi-
X. Tan, Q. Chang, F. Su et al. Journal of Molecular Liquids 346 (2022) 117879

Table 1
Mesophases, transition temperatures and transition enthalpy valuesa, lattice parametersb of diaminotriazine derivatives 0T3n and 2T3n.

Comp n T/°C [DH/kJ mol
1] a/nm (°C) n

12

0T3 12 Cr 77 [71.1] CubI/Pm 3 n 150 [0.1]Iso 9.39 (85) 74


0T314 14 Cr 50[13.2] CubI/Pm 3 n 127[0. 8]Iso 9.58 (85) 77


0T316 16 Cr 45 [40.0] CubI/Pm 3 n 126[0.3]Iso 9.67 (100) 82
2T310 10 Cr 95c Colhex 192[6.5] Iso 6.22 (100) 9.9
2T312 12 Cr 85c Colhex 177[0.4]Iso 6.53 (150) 10.0
2T314 14 Cr 76.4[14.1] Colhex180.5[2.66] Iso 6.54 (170) 9.7
2T316 16 Cr110[4.1]Colhex176[0.2]Iso 6.79 (130) 9.2


2T318 18 Cr 85[89.1]Colhex150 d
CubI/Im 3 m 200 Iso Col: 7.17 (100) 8.6
Cub: 8.09 (150) 126
a
Transition temperatures were measured


by DSC (see Fig. S2 and S4), and confirmed
by POM; values


in brackets are transition upon cooling; abbreviations:


Cr = crystalline
solid, I = isotropic liquid; CubI/Pm 3 n = micellar cubic mesophases with space group 3 n ; CubI/Im 3 m = micellar cubic mesophases with space group Im 3 m, respectively.
b
a = lattice parameter; n
=
number of molecules in the cross
section of a column in the Colhex phases (with assumed height of 0.45 nm) or number of molecules in each
aggregate of the cubic/Pm 3 n lattice (ncell/8) and the cubic/Im 3 m lattice (ncell/2), respectively.
c
Determined by optical investigation.
d
Determined by SAXS experiments.

cating that they are fluid liquid crystals (see Fig. S5). In Pm 3 n
phase, the molecules are organized into closed soft spherical
assemblies, with 8 such assemblies in each unit cell [11,12]
(Fig. 1b).
Five triple chain bisthiophenene compounds 2T3n (n = 10, 12,
14, 16, 18) with the longest core length were also prepared. Almost
all of them form exclusively columnar phase as confirmed by their
typical fan like textures (Fig. S6) except for 2T318. These columnar
phases are optically uniaxial, as supported by the completely dark
appearance, meaning the homeotropic alignment of the columns
(columns perpendicular to the glass substrates); while they are
optically negative, as shown by the investigation with a k-
retarder plate (insert of Figs S6a-c). This result implies that the
direction of the p-conjugation pathway in the molecule (i.e. the
long axis of the aromatic cores) is perpendicular to the long axis
of the columns on average.
The high-resolution small-angle X-ray scattering experiments
of 2T3n (see Figs. 2a, 3a, S8-S10, Table S4-S8) further confirmed
the columnar phase as a hexagonal Colhex/p6mm phase. Taking
2T310 as an example, the small-angle reflections of the mesophase
have a ratio of their reflection positions (10), (20), (21), (30) corre-
pffiffiffi
sponding to 1:2: 7:3 respectively, indicating a hexagonal lattice
(Colhex/p6mm). The symmetry is further confirmed by the grazing
incident small-angle X-ray scattering (GISAXS) in Fig. 2c. The mole-
cules’ number that organized in the cross section of the columns
with a height of h = 0.45 nm (maximum in diffuse wide-angle scat-
tering, distance between molecular layers from p-p interaction),
estimated using eq. (1) and supposing a density with q = 1 g/
cm3, is n = 9.9, 10.0, 9.7, 9.2, 8.6 for the investigated diaminotri-
azine 2T310, 2T312, 2T314, 2T316, 2T318 (NA = Avogadro constant,
M = molecular mass; see Table 1) respectively. Utilizing the
obtained n, molecular dynamics (MD) can be applied to verify
the molecular packing in hexagonal lattice as shown in Fig. 2d.
pffiffiffi
n ¼ ða2 =2Þ 3hðNA =MÞq
18
Interestingly, 2T3 first form a 2D hexagonal columnar phase
as other homologs (see Fig. 3a) at low temperature. Upon further
heating, a cubic phase appeared over 150 °C. The isotropic property


is determined by POM and space group is assigned as Im 3 m by
SAXS in Fig. 3b, c and Table S9. For such type of cubic phase, the
molecules are organized into spherical assemblies. There are 2
such assemblies in each unit cell. Such phase transition sequence
could be generated from the volume expansion of aliphatic chains,
which increases the curvature of the molecule leading to a phase


transition from 2D to 3D. Such aliphatic volume expansion can also
be found by WAXS (see Fig. S12), where the signal from aromatic
core distance vanished upon aliphatic chain elongation.
By comparison between compounds 0T3n and 2T3n, the influen-
tial factor on self-assembly structure can be derived. Compounds
0T3n have high chain density due to the dense packing of the alkyl
chains, and there is a high interface curvature because of the small
aromatic core, as it is usually the case for amphiphiles with small
head groups (carbohydrates, diols etc), therefore they all formed


micelles and organized into Pm 3 n phase, an answer to Kelvin
problem for minimum energy [13]. While bisthiophene series
(2T3n) has the longest aromatic core, with similar chain densities,
the aromatic-aliphatic interface curvatures decrease due to the
longer aromatic core, leading to less curved columnar phase as
shown in Fig. 4. Hence all compounds 2T3n form Colhex/p6mm
phase and only 2T318 with longest aliphatic tails form cubic phase
at high temperature.
3.2. Mesomorphic properties of monothiophene diaminotriazine
derivatives 1Tmn
The above investigation indicated that shorter or longer cores


are not suitable for the design of Im 3 m phase, therefore we turned
our attention back to the monothiophene series 1Tmn again, in
which four triple chain compounds 1T3n (n = 10,12,14,16) have
been investigated in our previously report [8], here more members
in this series namely two chains compounds 1T2n (n = 10,12,14,16)
and triple chain compounds 1T3n (n = 11,18) were synthesized.
Except compound 1T210 is a monotropic LC, all other double
chain compounds are enantiotropic LCs. Colhex/p6mm phase is
found in all 1T2n compounds (Fig. 5). These columnar mesophases’
textures are characterized with spherulitic domains with com-
pletely dark appearance of regions, and optically negative as sup-
ported by investigation with a k-retarder plate (insert of Fig. 5a,
Fig. S13). The hexagonal columnar phase of 1T2n is further investi-
ð1Þ gated by SAXS and WAXS (see Fig. 5b, Fig. S15-S18, Table S10-S13).
By calculation, the number of molecules organized in a slice of the
columns is about ten for the investigated double chain diaminotri-
azine compounds 1T2n (Table 2).
In the series of double chain compounds 1T2n with elongation
of peripheral chains, the formation of Colhex/p6mm phase requires
different environment. 1T210 is metastable and a decent scattering
pattern of hexagonal phase requires quench upon cooling at high
temperature. These requirements indicate the difficulty to obtain
liquid crystal phase for 1T210. Then for 1T212, though the hexago-
nal phase could form upon heating, it’s very hard to obtain pure
3
X. Tan, Q. Chang, F. Su et al. Journal of Molecular Liquids 346 (2022) 117879

Fig. 1. a) SAXS diffractogram
of the CubI/Pm 3 n of 0T312 at 85 °C, the ratio among all reflections is in line with Pm 3 n space group; b) reconstructed electron density (ED) map
of 0T312 showing typical Pm 3 n phase with high electron density in purple while low electron density region in red.

Fig. 2. a) SAXS diffractogram of hexagonal Colhex/p6mm phase of compound 2T310 at 100 °C; b) Reconstructed ED map for the Colhex/p6mm phase of compound 2T310 with
high electron density in purple while low electron density region in red; c) GISAXS pattern of 2T310 showing p6mm space group at T = 110 °C, distinct scales were applied for
clarity, scale for central region is  13 times stronger than outer region; d) Molecular dynamics (MD) simulation of the Colhex/p6mm phase formed by 2T310 with ten
molecules per lattice and same color code as ED map.

phase. One can only get a mixture of hexagonal LC and crystalline
verified by WAXS in Fig. S18. On the other hand, 1T214 and 1T216
with longer aliphatic tails exhibited proper liquid crystal property
in WAXS. This implies that aliphatic chains’ volume in 1T2n is not
small-angle X-ray scattering (GISAXS) pattern of the oriented 1T311
(Fig. 6b) also confirms the body-centered lattice with the space


group of 3 m. Hence, the cubic phase of compound 1T311 can be

enough to form 3D structures.
For the additionally synthesized triple chain compounds 1T3n
(n = 11,18), optically isotropic mesophases as typical for cubic
mesophases (Fig. S19) were detected under POM. The CubI phases
of compounds 1T3n (n = 11,18) were further investigated by SAXS
and GISAXS. For the CubI phases of compound 1T311, the reflection
pffiffiffi pffiffiffi
positions in the small-angle region are in a ratio of 1: 2: 3:2 cor-
responding to the reflection as (1 1 0), (2 0 0), (2 1 1), (2 2 0) (see
Fig. 6a), indicating a cubic lattice with a body-centered lattice as
all reflections of h + k + l = 2n + 1 are missing. The grazing incidence
indexed to the Im 3 m space group with a lattice parameter of
acub = 6.73 nm (Fig. S21, Tables 2 and S14).
For the low temperature phase of compound 1T318, the posi-
tions of the sharp small-angle peaks are consistent with the


Im 3 m symmetry (acub = 7.46 nm) (Fig. S22(a, c, e), Table S15).
While the cubic phases’ diffraction patterns at higher temperature
are completely different, which were indexed to a cubic lattice


with Pm 3 n space group (acub = 11.55 nm) [14] (Fig. S22 (b, d, f),
Table S16). Interestingly, upon cooling from high temperature

4
X. Tan, Q. Chang, F. Su et al. Journal of Molecular Liquids 346 (2022) 117879

Fig. 3. a) SAXS diffractogram of hexagonal Colhex/p6mm phase of compound 2T318 at 100 °C. b) SAXS diffractogram of cubic CubI/Im 3 m phase of compound 2T318 at 150 °C,
inset is POM result at same temperature showing isotropic property and c) reconstructed ED map showing body-centered cubic phase.

Fig. 4. Schematic representation of 0T3n and 2T3n as well as their distinct self-assembly behavior. 0T3n with higher chain density form micelles and 2T3n with lower chain
density form columns.

5
X. Tan, Q. Chang, F. Su et al. Journal of Molecular Liquids 346 (2022) 117879

Fig. 5. a) Textures of the columnar phases as observed under POM for compound 1T210 cooling from isotropic state at 168 °C; inset shows the same region with k-plate; b)
SAXS diffractogram of hexagonal Colhex/p6mm phase of compound 1T210 at 170 °C upon cooling; c) reconstructed ED map of the Colhex/p6mm phase of 1T210; d) MD
simulation of Colhex/p6mm phase of 1T210.

Table 2
Mesophases, transition temperatures and transition enthalpy valuesa, lattice parameters b
of monothiophene diamine triazine derivatives 1Tmn.

1
Comp m n T/°C [DH/kJ mol ] a/nm (T/°C) n
1T210 2 10 Cr1 35.8[1.4] Cr2 177.9[25.9] Iso (176.5[1.1] Colhex/p6mm 160.8[20.9] Cr1 21.8[4.9]Cr2) 5.48 (170) 10.3
1T212 2 12 Cr1 38[6.9] Cr2 133.2[9.42] Cr3 171[21.5] Col hex/p6mm 183[1.1] Iso 5.75 (175) 10.4
1T214 2 14 Cr1 61.4[19.0] Cr2 115.2[2.6] Cr3 135.2[22.7] Cr4 160.8[31.6] Col hex/p6mm 180.9[1.6] Iso 5.90 (170) 10.2
1T216 2 16 Cr1 67[16.7] Cr2 153 [18.1]Col hex/p6mm 173[0.4] Iso 6.05 (170) 10.0
1T310 3 10 Cr 68[1.8] Col hex/p6mm 126 [0.7] Iso 5.45 (100) 8.3


1T311 3 11 Cr 94[9.5] CubI/Im 3 m 113 [0.1] Iso 6.73 (100) 104
12

1T3 3 12 Cr95 [0.9] CubI/Im 3 m 112.2[0.07] Iso 6.81 (100) 105



1T314 3 14 Cr97[1.8] CubI/Im 3 m 115 CubI/Pm 3 n 148[0.15]Iso 7.13 (100) 109
11.13 (120) 103



1T316 3 16 Cr52 [7.9] CubI/Im 3 m 115 CubI/Pm 3 n 140 Isoc 6.99 (100) 93
10.85 (120) 87



1T318 3 18 Cr46 [27.6] CubI/Im 3 m 150d CubI/Pm 3 n (140 LQC)e167 [0.1] Iso 7.46 (115) 111
11.55 (150) 103
a
Transition temperatures were


determined by DSC (see Fig. S6), and confirmed by POM;

values in brackets are transition upon cooling; abbreviations: Cr = crystalline solid,
I = isotropic liquid; CubI/Pm 3 n = micellar cubic mesophases with space groups Pm 3 n, respectively.
b
a = lattice parameter; n

=
number of molecules in the cross
section of a column in the Colhex phases (with assumed height of 0.45 nm) or number of molecules in each
aggregate of the cubic/Pm 3 n lattice (ncell/8) and the cubic/Im 3 m lattice (ncell/2), respectively.
c
Determined by SAXS experiments.
d
CubI/Pm3n will form once cooled down
from isotropic phase.

e
Only appear upon cooling from CubI/Im 3 m phase without melt. LQC is stable until 100 °C without phase transition to CubI/pm 3 n phase.

CubI/Pm 3 n phase, compound 1T318 formed rarely found liquid with each other to achieve lowest energy. In our case, Im 3 m phase


quasicrystal (LQC) (Fig. S23, Table S17) [15]. is composed by truncated octahedra and Pm 3 n phase consists two
Therefore, all compounds 1T3n with short alkyl chains (n = 10, distinct polyhedrons, dodecahedra and CN14, a polyhedron con-


11, 12) form Im 3 m phases. For the longest chain compound structed by 12 pentagons and 2 hexagons. Originating from the


1T318, the thermostable Pm 3 n phase becomes dominating, the center of the polyhedrons, volume of micelle will increase freely

first and then restricted by polyhedral surface. The volume varia-
Im 3 m phase is a metastable phase. Similar to previous study, a tion trend, dV/dr, where V is micellar volume and r is the micellar


special LQC phase is related with CubI/Pm 3 n phase, which is stable radius, could specify the molecular shape requirement of different



over 40 °C [16]. The domination of Pm 3 n phase for longer aliphatic polyhedrons. Following the computation, Pm 3 n phase requires


tails can be well explained via the volume increase in micelles. As longer aliphatic tails compared with Im 3 m phase [16], besides,
reported before [8,16], in micellar cubic phase, all spherical/- Ungar et al proposed a rational interpretation of the effect of the
spheroidic assemblies are soft spheres, which will closely attach
6
X. Tan, Q. Chang, F. Su et al. Journal of Molecular Liquids 346 (2022) 117879

Fig. 6. a) SAXS diffractogram of cubic CubI/Im 3 m phase of compound 1T311 at 100 °C; b) GISAXS pattern with Im 3 m space group, which is well fitted to simulated pattern.
Different scales were applied for clarity.

number of chains on the phase type, sphere size, interdigitation etc
of micellar cubic phase [17], which could explain the domination of


n
Pm 3 n phase in 1T3 compounds with longer aliphatic chains. In


the perspective of temperature dependence, Pm 3 n phase is always

After a thorough research of rTmn compounds, the phase beha-
observed on higher temperature compared with Im 3 m phase. As
suggested before [8], such transition sequence can be resulted from
the stronger intercalation of aromatic cores upon heating. The
solution to Kelvin problem. Also, both the second order phase tran-


sition between Pm 3 n and LQC phase and the LQC stability upon
cooling indicate that LQC phase is more favorable when the volume
of aromatic cores expands.
viour is summarized in Fig. 7. As the aromatic core size increases
from 0T to 2T, the dominating phase transforms from cubic

stronger intercalation shrinks the micellar volume, i.e. dV/dr curve
with weaker peak/shorter tail. A combination of stronger aromatic
core intercalation and aliphatic chain folding at high temperature

phase. It’s evident that the molecular curvature determined by vol-
could fit the molecular curvature to the requirement of Pm 3 n


phase instead of Im 3 m phase. Besides, the LQC phase observed


upon cooling from Pm 3 n phase suggests the LQC might be a better
Pm 3 n phase to Im 3 m phase and finally p6mm columnar phase.
Besides, when core size is same as 1T, removing one aliphatic chain
would directly lead to the phase transition from cubic to columnar
ume ratio of aromatic/aliphatic part is critical to self-assembly
structure. Larger aromatic core and shorter alphatic chain con-
tribute to the formation of 2D hexagonal columnar phase. On the

Fig. 7. The phase transitions of compounds rTmn.

7
X. Tan, Q. Chang, F. Su et al. Journal of Molecular Liquids 346 (2022) 117879

Fig. 8. a) UV–Vis spectra of rT314 in CH2Cl2 solution and in film; b) Fluorescence spectra of rT314 in CH2Cl2 solution and in film (the inset showed the photos of solution of
rT314 under illumination of 365 nm lamp).

Table 3
UV–vis absorption and fluorescence spectroscopy data of rT314.

Comp. State Abs kmax/nm PL kmax/nmb UFLc Stokes shift(nm)d Eopt

g (ev)
e

14 a
0T3 DCM 282 343 0.14 61 3.88
Film 279 340 61
1T314 DCM 349 424 0.58 75 3.27
Film 342 416 74
2T314 DCM 393 485 0.85 92 3.07
Film 382 476 94
a
c = 1  10-5 M in CH2Cl2.
b
Excited at absorption maxima band.
c
Stcokes shifts = kem-kex.
d
relative to anthracene in 5.61  10-6 M EtOH (UF = 0.27).
e
The energy gap is calculated by the UV–vis absorption spectrum in the film state.

Fig. 9. Polarized FL spectra of light-emitting LC cell of TEB300 + 0.1 wt% 2T314: a) in electric field-off; b) electric field-on states (1KHz, 20 V). The dichroic ratio (NF) was
determined by the following formula: NF = F///F\, where F//and F\ are the rubbing direction of the LC cell perpendicular and parallel to the polarization direction of the
detector, respectively.

other side, smaller core and longer chain favor 3D cubic Pm 3 n


phase. And cubic Im 3 m phase, as an intermediate one, requires
precise design of the molecular curvature and temperature.
3.3. Photophysical properties
The UV–vis and fluorescence (FL) spectra of representative com-
pounds 0T314, 1T314and 2T314 were studied (Fig. 8, Fig. S24). The

8
X. Tan, Q. Chang, F. Su et al.
Fig. 10. a) Photos of the LE-LCD devices fabricated with light-emitting LC mixture (TEB300 + 0.1 wt% 2T314) in electric field-off and field-on status; b) Schematic
representation of the setup of the LE-LCD device with patterned alignment in the electric field-off and field-on states using the LC mixture.
UV–vis spectra of 0T314, 1T314 and 2T314 in DCM displayed a max-
imum peak at 282, 349 and 393 nm, respectively. While the thin
film’s UV–vis spectra of 0T314, 1T314 and 2T314 showed a maxi-
mum peak at 279, 342 and 382 nm respectively. The peaks are
slightly blue-shifted in films, this suggested a H-type parallel, that
is, the rigid core is arranged face to face [18]. By comparison, with
the increase of the conjugation length (from 0T314, 1T314 to 2T314),
the peaks of compounds show obviously red shifted in both UV–vis
and fluorescence spectra, and increasing values of the Stokes shift
(Table 3).
The photoluminescence quantum yield (UFL) values (Table 3,
measurement and calculation see SI) showed a dramatic increase
with increasing the number of thiophene in the rigid core of the
diamnine triazine derivatives, nonthiophene compound 0T314
(0.14), monothiophene compound 1T314 (0.58) and the dithio-
phene compound 1T314 (0.85). In this case, with increasing the
conjugation length via increasing the number of thiophene units,
the fluorescence quantum yield is largely enhanced.
3.4. Polarized emission spectra, the dichroic ratio and LE-LCD device
So far to our knowledge, no triazine derivatives have been
tested to fabricate LE-LCD. 2T314 is a strong fluorescent compound,
to assess its potentials as LE-LCD, it was doped with commercially
nematic liquid crystal TEB300 (TEB300 + 0.1 wt% 2T314). The
dichroic ratio of polarized fluorescence spectra [19] was measured
to be 5.8 in the electric field-off state (Fig. 9a) and about 1 in the
electric field-on state (Fig. 9b). According to this polarized fluores-
cence measurement, the LC mixture of 2T314 and commercially
available nematic LCs TEB300 was tested for fabrication of the
LE-LCDs. Firstly, patterned ITO glass substrate was prepared as
the LC cell. Then the unidirectional alignment of LC mixture was
obtained through rubbing the polyimide (PI) alignment layer (the
details for device fabrication are shown in SI). In order to examine
9
Journal of Molecular Liquids 346 (2022) 117879
the performance of the device, a UV lamp was applied as a light
source to irradiate the mixture material, and a polarizer with the
transmission direction parallel to the LC aligned direction was
applied to detect the change of PL efficiency. In the electric field-
off state, there would be a bright image in the cell under UV illumi-
nate. While when an electric field (1 KHz, 20 V) was imposed to the
LC cell, the area without ITO was detected to be light emissive. In
Fig. 10, the LE-LCD manufactured with a mixture of TEB300 + 0.1
wt% 2T314, showed the switching from almost bright to dark green
status as observed by naked eyes.
4. Conclusions
Therefore, three series of diaminotriazine derivatives with dif-
ferent core length have been investigated. For short core series


0T3n, Pm 3 n phase is formed. This is ascribed to their shorter aro-
matic cores, leading to high chain density and high interface curva-
ture. For the longest core series 2T3n the p6mm phase is
dominating due to the much longer rigid core and the reduced


interface curvature. Im 3 m phase is mainly observed in 1T3n series.


The critical point of Im 3 m phase formation is a proper curvature
control for single molecules as well as the influence of intercala-
tion. Besides, with specific molecular curvature, a rare liquid qua-
sicrystal was discovered, suggesting a rather complex phase
transition sequence and potential solution to Kelvin problem. A
temperature sensitive, aromatic-intercalation controlled reversible


phase transition between Pm 3 n and LQC phase is discovered.
Finally, we have realized for the first time for the practical applica-
tion of such rod-like diaminotriazine compounds 2T3n as LE-LCD
device. Thus, this work gives a deep insight into the relationship



between molecular structure and the formation of Pm 3 n/Im 3 m
phases, and contributes to the investigation of the formation of
even more complex structure by controlling molecular parameters.
X. Tan, Q. Chang, F. Su et al.
CRediT authorship contribution statement
Xiaoping Tan: Data curation. Qing Chang: Data curation. Fawu
Su: Investigation. Yu Cao: formal analysis, writing-original draft.
Feng Liu: writing-review and editing. Xiaohong Cheng: Writing-
original draft.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (No. 21865038) and the Natural Science Founda-
tion of Chongqing (No. cstc2020jcyjmsxmX0341). The authors
thank Prof. Yumei Zhang at the College of Materials Science and
Engineering, Donghua University, China, for allowing use of their
Material Studio (Accelrys Inc.). We also thank beamline BL16B1
at Shanghai Synchrotron Radiation Facility for providing
beamtimes.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.molliq.2021.117879.
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