Perylene liquid crystals with multiple alkyl chains: Investigation of the influence of peripheral alkyl chain number on mesomorphic and photophysical properties

Article abstract of DOI:10.1039/c8nj00480c

Herein, a series of mesogenic perylene bisimide (PBI) dyes including 1,6,7,12-tetrachloroperylenebisimides 11a, 11b and 11c with 2, 4 and 6 peripheral alkyl chains at the imide positions and 1,6,7,12-tetra-p-nonylphenol bay-substituted perylene bisimides 12a, 12b and 12c with 6, 8 and 10 peripheral alkyl chains at both the imide and bay-positions were synthesized and characterized. The influence of multiple peripheral alkyl chains on the mesomorphic and photophysical properties was investigated. The results suggested that all of them possessed hexagonal columnar mesophases. The presence of more alkyl chains contributed to lower phase transition temperature and more orderly hexagonal mesophases. These novel perylene liquid crystals exhibited excellent fluorescence properties with fluorescence quantum yields of 0.90-0.96 in solution. The compounds 12a, 12b and 12c presented larger Stoke shifts and higher Φ_F values than the compounds 11a, 11b and 11c; this indicated that more peripheral alkyl chains at both the imide and bay-positions contributed to the excellent fluorescence properties in both solution and thin films.

Full text of DOI:10.1039/c8nj00480c

View Article Online
View Journal
NJC
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: M. Zhu, Y. Chen,
H. Guo, F. Yang and X. Song, New J. Chem., 2018, DOI: 10.1039/C8NJ00480C.
Volume 40 Number
1
January 2016 Pages 1–846
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
NJC
New Journal of Chemistry
www.rsc.org/njc
A journal for new directions in chemistry
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
rsc.li/njc

Page 1 of 8
Pl
N
ea
e
s
w
e
J
d
o
o
u
n
rn
o
a
t
l
a
o
d
f
j
C
us
h
t
e
m
m
a
is
rgins
t
r
y
View Article Online
DOI: 10.1039/C8NJ00480C
Journal Name
ARTICLE
Perylene liquid crystals with multiple alkyl chains: Investigation of
the influence of peripheral alkyl chain numbers on mesomorphic
and photophysical properties
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
a
a
a
a,b
a
Mingguang Zhu, Yongzhu Chen, Hongyu Guo,* Fafu Yang,* and Xuchun Song
www.rsc.org/
Series of mesogenic perylene bisimide (PBI) dyes, including 1,6,7,12-tetrachloroperylenebisimides 11a, 11b and 11c with 2,
4
and 6 peripheralalkyl chains at the imide positions, and 1,6,7,12-tetrap-nonylphenol bay-substituted perylene bisimides
2a, 12b and 12c with 6, 8 and 10 peripheralalkyl chains at the both imide and bay-positions were synthesized and
1
characterized. The influence of multiple peripheralalkyl chains on mesomorphic and photophysical properties were
lucubrated. The results suggested that all of them possessed the hexagonal columnar mesophases. The more alkyl chains
contributed to the lower phase transition temperature and the more orderly hexagonal mesophase. These novel perylene
liquid crystals exhibited excellent fluorescence properties with the fluorescence quantum yields of 0.90-0.96 in solutions.
F
Compounds 12a, 12b and 12c presented the larger Stoke shifts and higher Ф values than compounds 11a, 11b and 11c,
indicating that the more peripheral alkyl chains at the both imide and bay-positions contributed to the more excellent
fluorescence properties in both solutions and thin films.
3
8
39
ethyleneoxide and dendritic peptides moieties. These literatures
revealed that the mesomorphic properties of PBI-based LCs could
be mediated effectively by the numbers and structures of the soft
chains at the imide substitutions, but the photophysical properties
were not influenced significantly due to the same aromatic
conjugated perylene skeleton. Recently, some PBI-based LCs with a
alkoxyl-aryl groups at the bay-area were reported, their
mesomorphic and photophysical properties could be tuned by the
substitution pattern, numbers and structures of grafting
1
. Introduction
Perylenebisimide (PBI) derivatives, as remarkable building blocks in
1
the supramolecular materials, were excellent candidates for
discotic liquid crystals (LCs), based on the effective intermolecular
π–π interactions for high processability and self-healing
2
,3
properties. Numerous functional perylene liquid crystals with
outstanding photophysical properties attracted much attention in
the development of new organic materials, such as organic solar
3
,25,40-49
4
-7
8,9,10
groups.
bearing six peripheral alkyl substituents at the both imide and
,6,7,12-bay positions, where four p-nonylphenol moieties were
Most lately, we reported the first perylene LCs
cells (OSCs), semiconductors,
and organic light emitting
11-18
diodes (OLEDs).
Naturally, an increasing number of seminal
1
perylene-based LCs were lucubrated extensively by the facile
chemical modifications with flexible units appended to different
sites on the perylene backbone. For examples, alkyl, alkoxy, 4-
cyanobiphenyl, triphenylene, cholesterol and pentaalkynylbenzene
units attached on the four ortho-positions of perylene core
successfully formed non bay-substituted and bay-annulated
grafted skillfully at the bay-positions of the PBI core. The p-
nonylphenol bay-substituted perylene LCs showed highly ordered
hexagonal columnar mesophase and excellent fluorescence with
large Stokes shift by comparison with previous perylene liquid
5
0
crystals. This research indicated that the modification of multiple
peripheral alkyl chains at the both imide and 1,6,7,12-bay positions
was a valuable strategy to achieve novel perylene LCs with excellent
mesomorphic properties and fluorescent properties. But this kind of
34 PBI-based LCs was almost unexplored besides this example. With
37 this in mind, in this paper, a series of PBI-based LCs with multiple
peripheral alkyl chains (2, 4, 6, 8, 10 chains, respectively) at the
both imide and 1,6,7,12-bay positions were prepared in 60-75%
yields. Moreover, this research provided a systematical and detailed
understanding of the relationship in the number changes of the
peripheral alkyl chains on mesomorphic and photophysical
properties for the first time. The results suggested that four p-
nonylphenol units at the bay-positions enhanced the fluorescence
with large Stoke shift and decreased the phase transition
1
1,19-27
perylenetetraesters for LCs.
In general, PBI-based LCs were
easily prepared by embellishing bisimide positions with the soft
2
8
29
30
groups, such as alkoxy, gallic acid amides, siloxane, 3,4,5-
3
1
32,33
tridodecyloxyphenyl,
triphenylene,
cyclotetrasiloxane,
3
5
36
oligosiloxane,
swallow-tail, polyhedral oligosilsesquioxane,
a.
College of Chemistry and Materials science, Fujian Normal University, Fuzhou
50007, P. R. China; Email: yangfafu@fjnu.edu.cn.
Fujian Key Laboratory of Polymer Materials, Fuzhou 350007, P. R. China.
3
b.
†
Footnotes relaꢀng to the ꢀtle and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 2 of 8
View Article Online
DOI: 10.1039/C8NJ00480C
ARTICLE
Journal Name
temperature. The more alkyl chains resulted in the higher
The structural characterizations of all new compounds were
unambiguously supported by NMR, MALDI-TOF MS and elemental
analysis (see the Supporting Information, SI, for the details). The
strong molecular ion peaks in MS spectra were in accordance with
51
fluorescence and the lower phase transition temperature.
1
2
. Results and discussion
the expected structures. All of the shifts and integrals in the H NMR
spectra agreed with the corresponding structures. For example, the
ArH on perylene skeleton of compounds 11a-11c and 12a-12c
showed one singlet with the most downfield shifts of ca. 8.66 ppm
and 8.18 ppm, respectively, although the peaks of compounds 12a-
2
.1. Synthesis and characterization
Although some dendritic perylene LCs with multiple alkoxy-
5
2-56
aromatic amide group at imide positions were reported,
no
perylene LCs consisting of four alkyl substituents at the bay-
positions and multiple alkyl groups at the imide positions, was
lucubrated systematically. In order to study the influence of
peripheralmultiple alkyl groups at the both imide and bay-
positionson mesomorphic properties and photophysical properties,
series of novel perylene derivatives were designed and synthesized
as shown in Scheme 1. Aromatic amide derivatives 3, 6 and 9
bearing one, two or three dodecanyl were prepared by
etherification of compounds 1, 2 or 3 and then ammonolysis with
ethylenediamine, their yields were over 80%. Subsequently, by
treating 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic
acid bisanhydride with compounds 3, 6 or 9 in dry DMF at 90 °C
for 12h, the corresponding perylene bisimides 11a, 11b, 11c (with 2,
1
2c became broad due to the influences of 6-10 alkyl chains. The
13
signals of C NMR and elemental analysis were also supported their
structures. It was worthy of noting that compounds 12a-12c were
the first examples of perylene derivatives with 6-10 peripheral alkyl
chains at the both imide andbay-positions on the perylene
o
backbone. The IR spectra of compound 12b were studied at 30 C
o
and 80 C as representative one (Figure S26 in SI). The results
-1
-1
suggested that the N-H bond shifted from 3381 cm to 3411 cm ,
suggesting the existence of hydrogen bond for N-H bond which was
favorable for the columnar phases.
2
.2. Mesomorphic studies
4
7
K
, and 6 alkyl chains, respectively) were obtained in yields of 69%-
5%. Finally, by reacting p-nonylphenol with compounds 11a 11c in
CO / NMP system at 130 °C, the red perylene derivatives 12a
2c with 6, 8 and 10 alkyl chains were isolated after purification by
-
cooling
heating
2
3
-
6
4
2
0
11a
1
chromatographic column in yields of 60–68%, respectively.
cooling
heating
11b
cooling
heating
11c
0
50
100
150
200
250
300
350
o
Temperature ( C)
Figure 1. The DSC traces of compounds 11a, 11b and 11c upon
-1
second heating and first cooling cycles at 5 °C min
2
cooling
heating
1
2a
0
2
4
cooling
heating
1
2b
-
-
cooling
1
2c
heating
0
50
100
150
o
200
250
Scheme 1. The synthetic routes for PBIs 11a-11c and 12a-12c: a)
N,N-dimethylformamide (DMF), 90°C, 12 h, yields: 75% (11a), 72%
Temperature ( C)
(
8
11b), 69% (11c); b) N-methyl-2-pyrrolidone (NMP), K CO
h, yields: 68% (12a), 70% (12b), 74% (12c).
2 3
, 130 °C, Figure 2. The DSC traces of compounds 12a, 12b and 12c upon
-1
second heating and first cooling cycles at 5 °C min
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 8
New Journal of Chemistry
Please do not adjust margins
View Article Online
DOI: 10.1039/C8NJ00480C
Journal Name
ARTICLE
The thermotropic liquid crystalline properties were investigated birefringent mesophase textures for these preylene derivatives
with the help of differential scanning calorimetry (DSC), polarizing appeared gradually. Figure 3 illustrated the textures of compounds
optical microscope (POM) and X-ray diffraction (XRD) analysis. 11a-11c and 12a-12c at corresponding temperatures. One can see
Figure 1 and 2 illustrated the DSC traces for compounds 11a-11c that these textures were the typical pseudo focal conic textures,
and 12a-12c, respectively. The phase transition temperatures and indicating the presence of columnar mesophases, which were
corresponding enthalpy values derived from the DSC thermograms further supported by following XRD analysis.
of second heating and first cooling cycles were minutely
summarized in Table 1. For example, compound 12b showed two
reversible phase transition at 56.5 °C and 177.8 °C on heating,
suggesting the transition of solid state-mesophase at 56.5 °C and
the transition of mesophase-isotropic phase at 177.8 °C. Also, the
peaks on cooling at 160.5 °C and 54.2 °C indicated the phase
transition of isotropic phase-mesophase and mesophase-solid state,
respectively. These DSC data certainly implied that compound 12b
have the reversible phase transition of solid state-mesophase and
mesophase-isotropic phase on cooling and heating. The DSC peaks
for other compounds exhibited the similar phase changes as that of
compound 12b. All these DSC results suggested that they had liquid
crystalline phases upon heating and cooling with the phase
transition process of crystal phase-mesophase-isotropic phase. The Figure 3. The mesophase textures of compounds 11a-11c at 120 °C
hysteresis phenomena were observed, which could be ascribed to and 12a-12c at 80 °C observed under POM on cooling (×400).
the super-cooling for such viscous materials. On the other hand,
one can see that the melting points of these samples exhibited the
In order to further elucidate the molecular stacking behaviors
order of 11a>11b>11c and 12a>12b>12c. Moreover, the melting in mesophases, the XRD experiments of compounds 11a-11c and
points of samples 11a-11c were higher than that of 12a-12c. 12a-12c were investigated at corresponding temperatures and their
Especially, sample 12c displayed the mesophase at room XRD curves were shown in Figure 4 and 5. One can see that all of
temperature on cooling. After calculation, the temperature scopes them exhibited similar reflection signals with three peaks at small
of mesophases for samples 11a-11c and 12a-12c were as wider as angle region, and the broad halos and a weak peak at wide angle
1
29-140 °C and 112-130 °C, respectively. These analyses indicated region. The compounds 11a (11b or 11c) presented the peaks at
o o o o o o o
that the more alkyl chains on perylene LCs contributed to the lower small angle of 3.68 (3.53 or 3.45 ), 6.38 (6.12 or 5.98 ) and 7.37
o
o
phase transition temperature. The alkyl substituents at the bay- (7.06 or 6.90 ), respectively. Based on Bragg equation of d =
positions were favourable for decreasing the phase transition λ/(2sinθ), the d-spacings derived from these angles could be
temperature. The perylene LCs with alkyl substituents at the imide calculated as 23.99 Å (25.01 Å or 25.59 Å), 13.84 Å (14.43 Å or 14.78
positions and at the both imide andbay-positions exhibited wide Å) and 11.99 Å (12.51 Å or 12.80 Å), which were in accordance with
temperature scopes of mesophases ( > 100 °C).
the ratios of 1:1/√3:1/2 for (100), (110) and (200) reflections of the
hexagonal columnar LCs. Also, the corresponding reflections of
Table 1 Summary of the phase transition temperatures (°C) and compounds 12a (12b or 12c) were observed at 3.63 (3.42 or
o
o
o
o
o
o
o
o
o
corresponding enthalpies for compounds 11a, 11b, 11c, 12a, 12b,
3
.34 ), 6.29 (5.93 or 5.79 ) and 7.27 (6.85 or 6.69 ), indicating
the d-spacings of 24.32 Å (25.81 Å or 26.43 Å), 14.04 Å (14.89 Å or
5.25 Å) and 12.15 Å (12.89 Å or 13.20 Å), respectively. These data
[
a]
and 12c (obtained from DSC)
-
1
phase transitions and enthalpies ΔH (in parentheses) kJ·mol
Second heating cycle First cooling cycle
Iso 221.9(8.9) Col 75.1(14.6) Cr
Iso 197.7(8.6) Col
208.1(12.2) Iso Iso 200.1(11.8) Col
1
Comp.
also agreed with the ratios of 1:1/√3:1/2 for (100), (110) and (200)
planes of the hexagonal mesophase. Furthermore, the broad halos
1
1a
1b
1c
Cr 87.2(13.1) Col
h
h
h
228.4(10.4) Iso
216.3(9.8) Iso
h
o
o
between 15 and 28 (the mean distance of 4.5 Å approximately)
were ascribed to the reflections of very short correlation length of
the molten peripheralalkyl chains. The weak reflections at wide
1
Cr 85.6(10.6) Col
Cr 80.0(14.3) Col
h
75.9(9.6) Cr
1
h
72.7(12.7) Cr
1
2a
2b
Cr 68.8(13.3) Col
Cr 56.5(14.4) Col
Cr 40.2(16.8) Col
h
h
h
198.1(6.9) Iso
177.8(5.2) Iso
151.6(4.5) Iso
Iso 186.6(6.2) Col
Iso 160.5(4.8) Col
Iso 141.9(4.8) Col
h
h
h
67.6(12.9) Cr
54.2(11.2) Cr
31.1(15.8) Cr
o
o
o
o
o
o
angles of 20.59 , 19.84 , 18.66 , 24.85 , 22.84 and 21.39 for
1
compounds 12a-12c and 11a-11c indicated the spacing of 4.31 Å,
1
2c
4
.47 Å, 4.75 Å, 3.58 Å, 3.89 Å and 4.15 Å, which were in agreement
[
a]
with the typical intracolumnar distance for the π-π interaction of
hexagonal columnar LCs. On the other hand, the (100) reflections of
compounds 11a and 12a were broader than that of other
compounds with more alkyl chains, suggesting the more peripheral
Values in the DSC thermograms obtained upon second heating
-1
and first cooling cycles at 5 °C min . Cr = crystal phase, Col
hexagonal columnar mesophase, Iso = isotropic phase.
h
=
Based on the DSC results, the discernible evolution of alkyl chains were favorable for the ordered hexagonal columnar LCs.
characteristic textures of the phase transitions of Iso-Col and Col-Cr Based on these data, the lattice parameter ɑ for compounds 11a-
phases for compounds 11a-11c and 12a-12c under POM were 11c and 12a-12c was calculated as 27.70 Å, 28.88 Å, 29.55 Å, 28.08
observed at their phase transition temperatures of DSC curves. By Å, 29.80 Å, and 30.52 Å, respectively. Thus, the average number (n)
annealing slowly to mesophase from the isotropic states, the
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 4 of 8
View Article Online
DOI: 10.1039/C8NJ00480C
ARTICLE
Journal Name
of molecules in one single disk for the column could be estimated Table 2 Summary of themesomorphic structures and lattice
parameters in the liquid crystalline phase for samples 11a, 11b, 11c,
12a, 12b, and 12c (obtained from XRD diffraction experiments)
by the following formula.
2
n = (ɑ )(√3/2)(hρN
where “ɑ” is the hexagonal lattice parameter, N
A
/M)
[a]
[b]
[c]
[d]
Comp.
T[°C]
120
120
120
80
phase
d
100[Å]
ɑ
hex[Å]
c [Å]
A
is Avogadro’s
number, M is the molecular mass of the compounds, the density (ρ)
1
1a
1b
Col
Col
Col
Col
Col
h
h
h
h
h
23.99
25.01
25.59
24.32
25.81
26.43
27.70
28.88
29.55
28.08
29.80
30.52
3.58
3.89
4.15
4.31
4.47
4.75
3
is assumed as 1 g/cm . After calculation, the number (n) was near 1
1
(0.70, 0.80, 0.89, 1.30, 1.27 and 1.32 for compounds 11a-11c and
12a-12c, respectively). Thus, the possible molecular stacking modes
11c
of hexagonal columns for these novel perylene LCs were proposed
as Figure 6. All these above XRD analyses indicated that compounds
1
2a
2b
1
80
11a-11c and 12a-12c were hexagonal columnar LCs. The more alkyl
chains contributed to more highly ordered hexagonal mesophase.
12c
60
Colh
[
a]
[b]
Col
h
= hexagonal columnar mesophase.
Intercolumnar axis
[
c]
spacing d100 [Å]. Hexagonal lattice parameter ɑhex[Å], ɑhex
=
3
2
1
000
000
000
0
2
5.59
(4/3dꢂ ). Intracolumnar layer spacing c [Å].
[d]
√
ꢀ
ꢁꢁ
2
.3. Photophysical properties
25.01
3.99
It was expected that there must be a considerable difference in the
photophysical properties between compounds 11a-11c and p-
nonylphenol bay-substituted perylene 12a-12c due to the
difference of the substituents at the bay-positions 1, 6, 7, 12 of the
perylene core. Thus, their photophysical properties were studied
systematically. Compound 12b was chosen as the representative
one to investigate the absorption and fluorescence spectra in
different solvents (Figure S21 and S22 in SI). As can be seen, the
fluorescence spectra resembled the mirror image of the absorption
2
1
4.78
1
2.80
4
.15
3.89
1
4.43
1
2.51
1.99
1
3.84
1
3
.58
1
0
20
30
40
Scattering angle 2
θ
(degree)
-10
(
The values on peaks were the
d-spacings (10 m))
Figure 4. XRD traces for compounds 11a, 11b and 11c on cooling at spectra and the strongest fluorescence emission appeared in
120°C.
chloroform solution. Therefore, the absorption spectra and
fluorescence spectra of compounds 11a-11c and 12a-12c in
-5
chloroform solution (1.0 × 10 mol/L) were measured as exhibited
in Figure 7 and 8, respectively. The photophysical data were
summarized in Table 2.
2
6.43
4
2
000
000
0
2
5.81
0
0
.8
.6
1
1
1
12a
12b
12c
1a
1b
1c
1
5.25
3.20
1
4.75
2
4.32
1
2c
1
4.89
1
2.89
4.47
4.31
12b
1
4.04
1
2.15
12a
0.4
10
20
30
40
Scattering angle 2
θ
(degree)
-
10
(
The values on peaks were the d-spacings (10 m))
0
0
.2
.0
Figure 5. XRD traces for compounds 12a and 12b at 80°C and 12c at
0°C on cooling.
6
400
500
600
700
Wavelength (nm)
C9H19
C9H19
O O
O
N
O
O
N
O
Figure.7 UV-vis absorption spectra of compounds 11a-11c and 12a-
R
R
-5
1
2c in chloroform (1.0 × 10 M).
O O
¨»
The absorption spectra of both compounds 11a-11c and 12a-
2c exhibited similar three pronounced absorption bands
C9H19
C9H19
d100
1
d
110
associated with the perylene core π–π* transition of symmetrical
perylene bisimides in the visible range. When compared with the
parent derivatives 11a-11c, the absorption maxima of the p-
Figure 6. The proposed molecular stacking of hexagonal columns
for these novel perylene derivatives
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 8
New Journal of Chemistry
Please do not adjust margins
View Article Online
DOI: 10.1039/C8NJ00480C
Journal Name
ARTICLE
nonylphenol bay-substituted PBIs 12a-12c showed the
bathochromic shifts of ca. 67 nm. Moreover, the fluorescence Table 3 Summary of the photophysical properties of novel PBIs
[a]
[
b]
[c]
spectra of p-nonylphenol bay-substituted PBIs 12a-12c also
exhibited the large bathochromic shifts (ca. 75 nm) than
compounds 11a-11c. These bathochromic phenomena could be
attributed to the electron donating p-nonylphenol units at the bay-
positions increasing the intramolecular charge-transfer (ICT)
Sample
λabs
λem
Stokes shift
(nm)
ФF
ФF
(nm)
(nm)
(solution) (thin film)
1
1a
1b
524
523
524
591
591
590
551
551
551
626
625
626
27
28
27
35
34
36
0.90
0.92
0.92
0.94
0.94
0.94
0.01
0.03
0.05
0.11
0.13
0.16
1
11c
5
7,58
efficiency.
Another reason might be that the p-nonylphenol
1
2a
2b
units enlarged the conjugated system of perylene skeleton,
resulting in the red shift of fluorescence. The Stoke shifts of
compounds 12a-12c were 34-36 nm, which were obviously larger
than that of compounds 11a-11c (27-28 nm). On the other hand, all
of them possessed the high fluorescence quantum yields (0.90-0.94)
1
12c
[a]
Values for PBIs 11a-11c and 12a-12c determined in chloroform
1.0 × 10 M). Excited at the respective excitation 11a-11c (λex =
80 nm) and 12a-12c (λex = 550 nm). Values for the thin films were
-5
[b]
(
4
[c]
F
in solution and compounds 12a-12c presented higher Ф values obtained by exciting at 520 nm for 11a-11c and 580 nm for 12a-12c.
than compounds 11a-11c, indicating that the multiple chains groups
at the bay-positions were favourable for enhancing the
fluorescence properties. Moreover, the fluorescence experiments 3. Conclusions
showed that the fluorescence quantum yields kept stable at highest
In conclusion, series of 1,6,7,12-tetrachloroperylenebisimides
1a 11b and 11c with 2, 4 and 6peripheral alkyl chains at the
imide positions, 1,6,7,12-tetrap-nonylphenol bay-substituted
perylene bisimides 12a 12b and 12c with 6, 8 and 10
-5
-6
values (0.90-0.94) from concentrations of 1.0 × 10 M to 1.0 × 10
1
,
-5
M. When the concentrations were bigger than 1.0 × 10 M, the
fluorescence quantum yields decreased gradually. At last, the
quantum yields were as low as 0.01-0.16 for solid films, which could
be attributed to the influences of ACQ effects of strong π-π stacking
of perylene skeleton. Although compounds 11a-11c exhibited very
weak fluorescent emission in thin films, p-nonylphenol bay-
substituted perylene 12a-12c showed the remarkable fluorescent
,
peripheral alkyl chains at the both imide and bay-positions
were prepared in yields 60%-75%. The investigation of their
mesomorphic properties suggested that all of them formed
thermotropic hexagonal columnar liquid crystalline phases.
The more peripheral alkyl chains contributed to the lower
phase transition temperature and more orderly hexagonal
mesophase. The studies on photophysical properties indicated
that all of them had excellent fluorescence properties.
F
enhancement with Ф values of 0.11-0.16. The UV-vis spectra and
fluorescence spectra of samples 11b and 12b in solid films were
investigated as representative ones (in SI Figure S24 and S25). Both
samples 11b and 12b exhibited the obvious red shift for absorption
and fluorescence spectra in comparison with the spectra in
solution. The sample 11b showed the larger red shift than sample
Compounds 12a
and the higher fluorescence quantum yields than compounds
1a 11b and 11c. The more peripheral alkyl chains at the both
, 12b and 12c exhibited the larger Stoke shifts
1
,
12b, indicating the stronger π-π stacking action of 11b than 12b.
imide and bay-positions were favourable for increasing the
fluorescence quantum yields in both solutions and thin films.
These phenomena could be explained by that the bay-substitutions
produced strong steric hindrance, which reduced the ACQ effect of
π-π stacking of perylene skeleton. All these photophysical analysis
suggested that both compounds 11a-11c and 12a-12c had good
fluorescence properties, and the more peripheralalkyl chains at the
both imide andbay-positions resulted in higher the fluorescence
quantum yields in both solutions and thin films.
4
. Experimental Section
4
.1. General
All solvents and reagents were obtained from commercial suppliers
and used as received without further purification, unless otherwise
stated. Commercially available reagent grade solvents were distilled
before use. Dry N,N-dimethylformamide (DMF) and N-methyl-2-
pyrrolidone (NMP) were prepared by treatment with molecular
sieve. Column chromatography was performed on silica (silica gel,
8
6
4
2
00
00
00
00
0
1
1
1
12a
1
1
1a
1b
1c
2b
2c
2
00-300 mesh). Thin-layer chromatography (TLC) was performed on
glass plates precoated with silica gel. Nuclear magnetic resonance
NMR) spectra were obtained in CDCl on a Bruker-ARX 400
spectrometer. Chemical shifts were quoted in parts per million
ppm) from tetramethoxysilane (TMS) as the internal standard. High
(
3
(
resolution mass spectra were measured on an MALDI-TOF-MS
mass spectrometer from Bruker Daltonics. UV-vis absorption
spectra (UV-vis) were recorded on a Varian spectrophotometer.
Fluorescent spectra were carried out on a Varian CARY Fluorescent
spectrophotometer with a bandwidth of 3 nm for excitation and
5
00
550
600
650
700
750
800
Wavelength (nm)
-
5
Figure.8 Fluorescence emission spectra in chloroform (1.0 × 10 M)
for 11a-11c (λex = 480 nm) and 12a-12c (λex = 550 nm).
F
emission. The fluorescence absolute Φ values were obtained on an
Edinburgh Instruments FLS920 Fluorescence Spectrometer with a 6-
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 6 of 8
View Article Online
DOI: 10.1039/C8NJ00480C
ARTICLE
inch integrating sphere. The thermotropic properties were analyzed Compound 11a: Compound
Journal Name
3
(0.7 g, 2 mmol) and 1,6,7,12-
by differential scanning calorimetry (DSC) with heating and cooling tetrachloroperylene-3,4,9,10-tetracarboxylic acid bisanhydride
-
1
rates of 5 °C min under N
XRD) were performed on a SEIFERT-FPM (XRD7) diffraction meter
using Cu Kα radiation with 40 kV, 30 mA power. Mesomorphic disappearance of compound
textures were observed under a polarization optical microscope cooled to room temperature and poured into an ice-water
POM) Leica DMRX with a temperature-controlled THMS-600 hot mixture. The precipitate was collected, washed by the water,
stage. Compounds 8 and 9 were prepared according to the and separated by column chromatography (DCM/ethyl acetate
2
atmosphere. X-ray diffraction patterns (0.53g, 1 mmol) in 35 mL of dry DMF was stirred under
atmosphere at 90°C for 12 h. TLC detection suggested the
. The reaction mixture was
(
N
2
3
(
2
9
published methods.
(4/1, v/v)). The compound 11a was obtained as red solid in
1
yield of 75%. Compound 11a: H NMR (400 MHz, CDCl
3
) δppm:
4
.2. Synthesis of compounds 2 and 5
Compound : The mixture of methylparaben
-bromododecane (0.75 g, 3 mmol) and anhydrous K
g, 4 mmol) in 30 mL of dry MeCN were stirred and refluxed
under N atmosphere for 24 h. The TLC detection indicated the
.
8.66 (s, 4H, Per-H), 7.65 (d, J = 8.0Hz, 4H, Ar-H), 6.87 (d, J =
8
3
1
.0Hz, 4H, Ar-H), 6.68 (s, 2H, NH), 4.54 (t, J = 8.0Hz, 4H, NCH
.96 (t, J = 8.0Hz, 4H, Ar-OCH ), 3.89 (t, J = 8.0Hz, 4H, NHCH
.80~1.25 (m, 40H, CH ), 0.87 (t, J = 8.0Hz , 6H, CH
) δppm: 167.39, 163.18, 162.02, 135.70,
2
),
2
1
(0.30 g, 2 mmol),
CO (0.55
2
2
),
1
2
3
1
3
2
3
); C NMR
(
100 MHz, CDCl
3
2
1
6
2
1
C
33.29, 132.40, 131.46, 128.77, 126.09, 123.36, 122.91, 114.23,
8.28, 40.24, 39.78, 31.93, 29.85, 29.61, 29.37, 29.15, 26.01,
disappearance of the materials. Subsequently, the mixture was
cooled to room temperature and 100 mL of water were added
in it. The resulting precipitation was filtered and washed by
water (3×20 mL) for three times. The crude product was
2.71, 14.14; MALDI-TOF-MS Calcd. for
C
66
+
H
72Cl N
4 4
8
O ：
m/z =
1190.09 (M ). Anal. calcd for
66 4 4 8
H72Cl N O : C 66.55, H 6.09, N 4.70; found C 66.52, H 6.11, N
190.40. found: m/z
=
3
recrystallized in MeOH / CHCl (V/V=5:1) to give white powder
1
4.64.
in yield of 88%. Compound
.97 (d, J = 8.0 Hz, 2H, Ar-H), 6.89 (d, J = 8.0 Hz, 2H, Ar-H), 3.99
t, J = 7.8 Hz, 2H, Ar-OCH ), 3.87 (s, 3H, OCH ), 1.80~1.26 (m,
), 0.88 (t, J = 8.0Hz , 3H, CH ).
: The same procedure for preparing compound
were carried out to obtain compound by reacting methyl-
,5-dihydroxybenzoate (0.34 g, mmol) and 1-
bromododecane (1.5 g, 6 mmol) under the refluxing condition
of anhydrous K CO (1.1 g, 8 mmol) and dry MeCN (40 mL).
White compound was obtained in yield of 85%. Compound
H NMR (400 MHz, CDCl ) δppm: 7.16 (d, J = 8.0 Hz, 2H, Ar-H),
.63 (bs, 1H, Ar-H), 3.98 (m, 4H, Ar-OCH ), 3.91 (m, 3H, OCH ),
.79~1.26 (m, 40H, CH ), 0.88 (t, J = 8.0Hz , 6H, CH ).
3
2: H NMR (400 MHz, CDCl ) δppm:
Compounds 11b and 11c were synthesized by the same
7
procedure for preparing compound 11a. Compound 11b: 72%
1
yield. H NMR (400 MHz, CDCl
(
2
3
3
) δppm: 8.66 (s, 4H, Per-H), 6.79
20H, CH
2
3
(m, 6H, Ar-H and NH), 6.51 (s, 2H, Ar-H), 4.54 (t, 4H, J = 7.8Hz,
Compound
5
2
NCH
2
), 3.92 (t, 8H, J = 7.8Hz, OCH
), 1.77~1.25 (m, 72H, CH ), 0.86 (m, 20H, CH
C NMR (100 MHz, CDCl ) δppm: 167.96, 163.06, 160.35,
2
), 3.87 (t, J = 8.0Hz, 4H,
5
NHCH
2
2
2
and CH ).
3
3
4
2
1
3
3
1
1
36.29, 135.62, 133.27, 131.42, 128.78, 123.30, 123.00, 114.14,
05.13, 68.27, 40.23, 39.67, 31.93, 30.34, 29.65, 29.63, 29.53,
2
3
5
5:
1
29.37, 29.22, 26.06, 22.70, 14.14; MALDI-TOF-MS Calcd. for
+
m/z = 1558.82. found: m/z = 1558.70 (M ). Anal.
3
C
90
H
120Cl
4
N
4
O
10
:
6
1
2
3
calcd for C90H120Cl N O10: C 69.30, H 7.75, N 3.59; found C 69.35, H
4 4
2
3
1
.71, N 3.53. Compound 11c: 69% yield. H NMR (400 MHz,
7
CDCl
3
) δppm: 8.58 (s, 4H, Per-H), 6.97 (s, 2H, NH), 6.91 (s, 4H,
), 3.95 (m, 12H, OCH ), 3.78 (t, 4H,
), 1.81~1.24 (m, 120H, CH ), 0.85 (t, J = 8.0Hz, 18H, CH ).
C NMR (100 MHz, CDCl ) δppm: 167.73, 162.91, 152.99,
4
.3. Synthesis of compounds 3 and 6.
Ar-H), 4.47 (t, 4H, NCH
NCH
2
2
Compound
3: Compound 2 (0.69 g, 1 mmol) and 1 mL of
2
2
3
ethylenediamine were stirred and refluxed in 15 mL of 13
3
methanol for 8 h. TLC detection suggested the disappearance
1
40.89, 135.44, 132.97, 131.39, 129.05, 128.76, 123.34, 122.96,
05.38, 73.44, 69.13, 40.24, 39.69, 31.93, 30.34, 29.73, 29.68,
9.67, 29.47, 29.38, 26.19, 26.09, 22.69, 14.10; MALDI-TOF-MS
of compound 2. Then the solvent was distilled under vacuum
1
2
and the residue was recrystallized in MeOH/CHCl
3
(V/V=8:1).
Compound
Compound
3 was obtained as white soft solid in yield of 95%.
1
3: H NMR (400 MHz, CDCl
Calcd. for
+
C
114
H
4
168Cl N
4
O
12
:
m/z = 1927.18. found: m/z = 1927.66
3
) δppm: 7.74 (d, J = 8.0
(M ). Anal. calcd for C114
H168Cl N O12: C 71.00, H 8.78, N 2.91; found
4 4
Hz, 2H, Ar-H), 6.89 (d, J = 8.0Hz, 2H, Ar-H), 6.68 (s, 1H, NH),
C 71.04, H 8.73, N 2.87.
3
2
=
.98 (t, J = 8.0Hz, 2H, Ar-OCH
.93 (t, J = 8.0Hz, 2H, NCH ), 1.80~1.26 (m, 20H, CH
8.0Hz , 3H, CH ).
: The same procedure for preparing compound
was used for synthesizing compound . The white compound
was obtained in yield of 92%. Compound
CDCl ) δppm: 6.98 (s, 1H, NH), 6.90 (s, 2H, Ar-H), 6.53 (s, 1H,
Ar-H), 3.93 (t, J = 8.0Hz, 4H, Ar-OCH ), 3.46 (m, 2H, NCH ), 2.93
t, J = 7.8 Hz, 2H, NCH ), 1.77~1.19 (m, 40H, CH ), 0.86 (t, J =
2
), 3.48 (t, J = 8.0Hz, 2H, NCH
2
),
2
2
), 0.87 (t, J
4
.5. Synthesis of perylenebisimides 12a, 12b and 12c
Compound 12a: The mixture of compound 11a (0.595 g, 0.5
mmol), p-nonylphenol (0.66 g, 3 mmol), and K CO (0.42 g, 3
mmol) in 25mL of dry NMP was stirred under N atmosphere at
.
3
Compound
6
3
6
2
3
6
1
2
6
: H NMR (400 MHz,
1
30°C for 8h. TLC detection suggested the disappearance of
3
compound 11a. After cooling, 50 mL of HCl solution (1 M) was
2
2
added and the product was extracted with 40 mL of DCM. The
(
2
2
organic layer was washed by aqueous NaHCO
3
solution and
3
8.0Hz , 6H, CH ).
dried over anhydrous MgSO . After filtration, the solution was
4
concentrated and the residue was separated by column
chromatography (DCM/ethyl acetate (6/1, v/v)). Compound
4
.4. Synthesis of tetrachloroperylenebisimides 11a, 11b and
1c
1
.
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 8
New Journal of Chemistry
Please do not adjust margins
View Article Online
DOI: 10.1039/C8NJ00480C
Journal Name
2a was obtained as red solid in yield of 68%. Compound 12a
ARTICLE
1
1
:
4
5
J. Niederhausen, H. R. Kersell, C. Christodoulou, G. Heimel, H.
Wonneberger, K. Müllen, J. P. Rabe, S. Hla and N. Koch,
Langmuir., 2016, 32, 3587-3600.
J. Idé, R. Méreau, L. Ducasse, F. Castet, H. Bock, Y. Olivier, J.
Cornil, D. Beljonne, G. D’Avino, O. M. Roscioni, L. Muccioli
and C. Zannoni, J. Am. Chem. Soc., 2014, 136, 2911-2920.
O. Thiebaut, H. Bock, and E. Grelet, J. Am. Chem. Soc., 2010,
32, 6886-6887.
A.Wicklein,S. Ghosh, M. Sommer, F.Würthner and M.
Thelakkat, ACS Nano, 2009, , 1107-1114.
B. A. Gregg and M. E. Kose, Chem. Mater., 2008, 20, 5235-
5239.
S. Sergeyev, W. Pisula and Y. H. Geerts, Chem. Soc. Rev.,
H NMR (400 MHz, CDCl
8.0Hz, 4H, Ar-H), 7.20 (m, 8H, Ar-H), 6.84 (m, 14H, Ar-H and
NH), 4.46 (t, 4H, NCH ), 3.95 (m, 4H, OCH ), 3.79 (t, 4H, NHCH ),
.79~0.64 (m, 122H, CH ); C NMR (100 MHz, CDCl
δppm: 167.14, 164.08, 161.80, 155.93, 152.67, 132.71, 128.71,
3
) δppm: 8.20 (s, 4H, Per-H), 7.64 (d, J
=
2
2
2
1
3
1
2
and CH
3
3
)
6
7
8
9
1
1
1
1
2
1
C
28.30, 127.63, 126.15, 122.11, 120.53, 119.48, 119.39, 114.68,
14.11, 68.10, 40.69, 39.58, 31.95, 29.65, 29.39, 28.98, 26.05,
3
2.92, 14.16; MALDI-TOF-MS Calcd. for
C
126
H
164
N
4
O
12
:
m/z =
926.23. found: m/z = 1927.70 (M-H ). Anal. calcd for
12: C 78.55, H 8.58, N 2.91; found C 78.49, H 8.55, N 2.94.
+
126 164 4
H N O
2007, 36, 1902-1929.
0 M. Muth, G. Gupta, A. Wicklein, M. Carrasco-Orozco, T.
Thurn-Albrecht and M. Thelakkat, J. Phys. Chem. C, 2014, 114
Compounds 12b and 12c were synthesized by the same above-
described procedure in yields of 70% and 74%, respectively.
1
,
Compound 12b: 64% yield. H NMR (400 MHz, CDCl
3
) δppm:
9
2-102.
.19 (s, 4H, Per-H), 7.18 (m, 8H, Ar-H), 6.76 (m, 14H, Ar-H and 11 R. K. Gupta, D. Das, M. Gupta, S. K. Pal, P. K. Iyer and A. S.
NH), 6.50 (s, 2H, Ar-H), 4.42 (m, 4H, NCH ), 3.88 (t, 8H, J =
Achalkumar, J. Mater. Chem. C, 2017, , 1767-1781.
.8Hz, OCH ), 3.77 (m, 4H, NHCH ), 1.68~0.59 (m, 168H, CH
). C NMR (100 MHz, CDCl ) δppm: 167.71, 164.05,
8
5
2
1
1
2 S. Alibert-Fouet, S. Dardel, H. Bock, M. Oukachmih, S.
Archambeau, I. Seguy, P. Jolinat and P. Destruel,
7
2
3
2
2
1
and CH
3
3
ChemPhysChem, 2003,
3 J. Eccher, W. Zajaczkowski, G. C. Faria, H. Bock, H. von
Seggern, W. Pisula and I. H. Bechtold, Appl. Mater. Interfaces,
2015, , 16374-16381.
4 J.Eccher, G. C. Faria, H. Bock, H. von Seggern and I. H.
Bechtold, Appl. Mater. Interfaces, 2013, , 11935-11943.
4, 983-985.
160.25, 155.97, 152.80, 139.01, 136.35, 132.68, 128.25, 127.61,
122.18, 120.63, 119.46, 119.13, 114.56, 105.15, 68.19, 40.59,
39.60, 31.93, 29.68, 29.37, 29.15, 26.01, 22.70, 14.13; MALDI-
7
1
1
TOF-MS Calcd. For
+
C
150
H
212
N
4
O
14
:
m/z = 2294.65. found: m/z =
5
2
294.58 (M ).Anal. calcd for C150
212 4
H N O14: C 78.49, H 9.31, N 2.44;
5 I. Seguy, P. Jolinat, P. Destruel, J. Farenc, R. Mamy, H. Bock, J.
Ip and T. P. Nguyen, J. Appl. Phys., 2001, 89, 5442-5448.
1
found C 78.44, H 9.34, N 2.46. Compound 12c: 60% yield. H
NMR (400 MHz, CDCl
3
) δppm: 8.18 (s, 4H, Per-H), 7.18 (d, J = 16 S.Keuker-Baumann, H. Bock, F. D. Sala, S. A. Benning, T.
Haßheider, T. Frauenheim and H. Kitzerow, Liq. Cryst., 2011,
, 1105-1113.
17 I. Seguy, P. Destruel and H. Bock, Synthetic Metals, 2000, 111
5-18.
8
4
1
.0Hz, 8H, Ar-H), 6.88 (s, 4H, Ar-H), 6.79 (m, 10H, Ar-H and NH),
2
8
.43 (t, 4H, NCH
2
2 2
), 3.93 (m, 12H, OCH ), 3.77 (t, 4H, NCH ),
1
3
,
2 3 3
.72~0.60 (m, 214H, CH and CH ); C NMR (100 MHz, CDCl )
1
δppm: 167.53, 164.12, 156.11, 155.83, 152.90, 144.84, 140.75,
1
8 R. K. Gupta,H. Ulla, M. N. Satyanarayan and A. A. Sudhakar,
Eur. J. Org. Chem., 2018, DOI: 10.1002/ejoc.201800161.
1
1
2
29.07, 128.25, 127.59, 127.33, 122.20, 120.50, 119.08, 118.73,
05.23, 73.52, 68.85, 40.67, 39.95, 31.95, 30.34, 29.77, 29.73, 19 T. Hassheider, S. A. Benning, H. Kitzerow, M. Achard and H.
Bock, Angew. Chem. Int. Ed., 2001, 40, 2060-2063.
9.69, 29.63, 29.43, 29.40, 29.28, 26.12, 22.71, 14.14; MALDI-
2
2
2
2
0 S. K. Gupta, S. Setia, S. Sidiq, M. Gupta, S. Kumar and S. K.
Pal, RSC Adv., 2013, , 12060-12065.
TOF-MS Calcd. for
+
C
174
260
H N
O
4 16
:
m/z = 2663.09. found: m/z =
16: C 78.45, H 9.84, N
3
1 I. Bala, S. P. Gupta, J. De and S. K. Pal, Chem. Eur. J., 2017, 23
12767-12778.
2
663.31 (M ). Anal. calcd for C174
H
260
N
4
O
,
2.10; found C 78.49, H 9.80, N 2.14.
2 X.F. Kong, L.T. Xia, H.F. Zhang, S.P. Dai, C.L. Yu, Z. Liu, L.P.
Mu, G.X. Wang and Z.Q. He, RSC Adv., 2017, , 17030-17037.
3 R. K. Gupta, S. K. Pathak, B. Pradhan, M. Gupta, S. K. Pal and
7
Conflicts of interest
A. A. Sudhakar, ChemPhysChem, 2016, 17, 859-872.
24 R. K. Gupta, S. K. Pathak, B. Pradhan, D. S. S. Rao, S. K. Prasad
There are no conflicts to declare.
and A. S. Achalkumar, Soft matter., 2015, 11, 3629-3636.
5 J. Eccher, A. C. B. Almeida, T. Cazati, H. von Seggern, H. Bock
and I. H. Bechtold, J. Lumin., 2016, 180, 31-37.
6 R. K. Gupta, D. S. S. Rao, S. K. Prasad and A. S. Achalkumar,
Chem. Eur. J., 2018, 24, 3566-3575.
7 R. K. Gupta, B. Pradhan, S. K. Pathak, M. Gupta, S. K. Paland A.
A.Sudhakar, Langmuir, 2015, 31, 8092-8100.
8 K. Bijak, H. Janeczek, M. Grucela-Zajac and E. Schab-
Balcerzak, Opt. Mater., 2013, 35, 1042–1050.
2
2
2
2
Acknowledgements
Financial support from the National Natural Science
Foundation of China (No: 21406036), Fujian Natural Science
Foundation of China (No. 2017J01571) and the National
Undergraduate Innovation Program in Fujian Normal
University (2018) were greatly acknowledged.
29 L. Meng, Q.M. Wu, F.F. Yang and H.Y. Guo, New J. Chem.,
015, 39, 72-76.
0 T.J. Zhang, D.M. Sun, X.K. Ren, L.L. Liu, G.Y. Wen, Z.J. Ren,
H.H. Li and S.K. Yan, Soft Matter, 2013, , 10739-10745.
2
3
3
9
References
1 M. G. Debije, Z.J. Chen, J. Piris, R. B. Neder, M. M. Watson, K.
Müllen and F. Würthner, J. Mater. Chem., 2005, 15, 1270-
1276.
1
2
F. Würthner, Chem. Commun., 2004, 37, 1564-1579.
T. Wohrle, I. Wurzbach, J. Kirres, A. Kostidou, N. Kapernaum,
J. Litterscheidt, J.C. Haenle, P. Staffeld, A. Baro, F. 32 H.Y. Guo, M.G. Zhu, Z.S. Wang and F.F. Yang, Tetrahedron
Giesselmann and S. Laschat, Chem. Rev., 2016,116, 1139-
Lett., 2016, 57, 4191-4195.
1241.
Z.J. Chen, U. Baumeister, C. Tschierske and F. Würthner,
Chem. Eur. J., 2007, 13, 450-465.
33 Y.M. Xiao, X.L. Su, L. Sosa-Vargas, E. Lacaze, B. Heinrich, B.
Donnio, D. Kreher, F. Mathevet and A. Attias, CrystEngComm,
2016, 18, 4787-4798.
3
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 8 of 8
View Article Online
DOI: 10.1039/C8NJ00480C
ARTICLE
Journal Name
3
3
3
3
4 M. Funahashi, M. Yamaoka, K. Takenami and A. Sonoda, J.
Mater. Chem. C, 2013, 1, 7872-7878.
5 M. Funahashi, N. Takeuchi and A. Sonoda, RSC Adv., 2016, 6,
8703-18710.
1
6 A. Wicklein, A. Lang, M. Muth and M. Thelakkat, J. Am. Chem.
Soc., 2009, 131, 14442-14453.
7 H.J. Ben, X.K. Ren, B. Song, X.P. Li, Y.K. Feng, W. Jiang, E.Q.
Chen, Z.H. Wang and S.C. Jiang, J. Mater. Chem. C, 2017,
566-2576.
5,
2
3
3
4
4
4
4
4
4
4
4
4
8 J. V. Herrikhuyzen, A. Syamakumari, A. P. H. J. Schenning and
E. W. Meijer, J. Am. Chem. Soc., 2004, 126, 10021-10027.
9 B.X. Gao, D.F. Xia, L.C. Zhang, Q.Q. Bai, L.B. Bai, T. Yang and
X.W. Ba, J. Mater. Chem., 2011, 21, 15975-15980.
0 M.G. Zhu, H.Y. Guo, F.F. Yang and Z.S. Wang, RSC Adv., 2017,
7
, 4320-4328.
1 F. Würthner, C. Thalacker, S. Diele and C. Tschierske, Chem.
Eur. J., 2001, , 2245-2253.
2 M.G. Zhu, H.Y. Guo, F.F. Yang and Z.S. Wang, Dyes Pigm.,
016, 133, 387-394.
7
2
3 M.G. Zhu, Y.Z. Zhuo, K.C. Cai, H.Y. Guo and F.F. Yang, Dyes
Pigm., 2017, 147,343-349.
4 J. Kelber, M. Achard, F. Durola and H. Bock, Angew. Chem.
Int. Ed., 2012, 51, 5200-5203.
5 S.C. Chen, B.L. Hong, H.Y. Guo and F.F. Yang, Liq. Cryst., 2017,
DOI: 10.1080/02678292.2017.1383522.
6 M. M. Safont-Sempere, V. Stepanenko, M. Lehmann and F.
Würthner, J. Mater. Chem., 2011, 21, 72014-7209.
7 T.Z. Yang, J.L. Pu, J. Zhang and W.G. Wang, J. Org. Chem.,
2013, 78, 4857-4866.
8 Z. S. An, J. S. Yu, B. Domercq, S. C. Jones, S. Barlow, B.
Kippelen and S.R. Marder, J. Mater. Chem., 2009, 19, 6688-
6
698.
9 J. Kelber, M. Achard, B.G. Bonneval and H. Bock, Chem. Eur.
J., 2011, 17, 8145-8155.
0 M.G. Zhu, Y.Z. Zhuo, H.Y. Guo, F.F. Yang and J.B. Qiu, J.
Lumin., 2018, 194, 264-270.
1 S. K. Pathak, B. Pradhan, R. K. Gupta, M. Gupta, S. K. Pal and
4
5
5
5
5
5
5
5
5
5
A. S. Achalkumar, J. Mater. Chem. C, 2016, 4, 6546-6561.
2 S. Ghosh, X. Q. Li, V. Stepanenko and F. Würthner, Chem.
Eur. J., 2008, 14, 11343-11357.
3 X. Q. Li, X. Zhang, S. Ghosh and F. Würthner, Chem. Eur. J.,
2
008, 14, 8074-8078.
4 S. Ogi, V. Stepanenko, J. Thein and F. Würthner, J. Am. Chem.
Soc., 2016, 138, 670-678.
5 S. Ogi, V. Stepanenko, K. Sugiyasu, M. Takeuchi and F.
Würthner, J. Am. Chem. Soc.,2015, 137, 3300-3307.
6 X. Q. Li, V. Stepanenko, Z.J. Chen, P. Prins, L. D. A. Siebbeles
and F. Würthner, Chem. Commun., 2015, 42, 3871-3873.
7 C. C. Chao, M. K. Leung, Y. O. Su, K. Y. Chiu, T. H. Lin, S. J.
Shieh and S. C. Lin, J. Org. Chem., 2005, 70, 4323-4331.
8 M. J. Ahrens, M. J. Tauber and M. R. Waslelewski, J. Org.
Chem., 2006, 71, 2107-2114.
8
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins