From achiral to helical bilayer self-assemblies of a 1,3,5-triazine-2,4,6-triphenol-grafted polyanionic cluster: Countercation and solvent modulation

Article abstract of DOI:10.1039/c9dt01780a

A triazine derivative with two short alkyl chains was covalently grafted onto a disk-like polyoxometalate cluster on both sides, and an amphiphilic polyanionic cluster was obtained. The linear cluster complex showed phase separation in polar and non-polar

Full text of DOI:10.1039/c9dt01780a

View Article Online
View Journal
Dalton
Transactions
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: D. Liu, G. Zhang,
B. Gao, B. Li and L. Wu, Dalton Trans., 2019, DOI: 10.1039/C9DT01780A.
Volume 45 Number
1
7
January 2016 Pages 1–398
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Dalton
Transactions
An international journal of inorganic chemistry
www.rsc.org/dalton
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 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
rsc.li/dalton

Page 1 of 5
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
View Article Online
DOI: 10.1039/C9DT01780A
COMMUNICATION
From achiral to helical bilayer self-assemblies of 1,3,5-triazine-
,4,6-triphenol-grafted polyanionic cluster: Countercation and
2
solvent modulation
Received 00th January 20xx,
Accepted 00th January 20xx
Danjinkun Liu, Guohua Zhang, Bo Gao, Bao Li* and Lixin Wu
DOI: 10.1039/x0xx00000x
A triazine derivative with two short alky chains was covalently self-assembled structures.10 The synergistic effect of organic
grafted to a disk like polyoxometalate cluster on both sides, component helps assemblies of POM clusters under a controlled
generating an amphiphilic polyanionic cluster. The linear cluster state that the isolate one cannot conduct completely. Such an
complex showed phase separation in polar and non-polar ionic interaction, however, yields excessive flexibility and
consequently, some special assemblies with twisting packing
structure along a fixed direction become difficult in several
photo chromism and selective catalysis systems. For example,
very few examples dealing with asymmetric self-assembly of
ionic complexes were reported11 though the induced chirality of
organic cationic components can be easily transferred to POMs
via the electrostatic interaction. The reported results with chiral
structures were mainly from the individual behavior of
covalently grafted clusters.13 Beside lacunary POMs,14 the
Anderson-type cluster that possesses a disk like architecture in
solutions and self-assembled into spherical, planar, and helical
aggregates in turn with the solution polarity decreasing from
methanol/water to chloroform/n-hexane mixture. Accompanying
by morphologic change, the self-assembled bilayer structure
varied from regular bilayer with partial to full and over
interdigitation and finally turn to partial inverse interdigitation.
Meanwhile, induced chirality took place and was amplified in
helical assembly via the modulation of counter-cations and
solvent polarity.
12
Polyoxometalates (POMs) are a type of inorganic clusters with diameter of ca. 0.8 nm and thickness of 0.3 nm, has been
precise chemical composition and uniform size and topology.1 demonstrated to have outstanding features differing from many
Due to the important physical and chemical properties sourcing other POMs, since this kind of clusters can also be conveniently
from metal elements and oxidized state, heteroatom, and cluster modified with triol ligands covalently.15 The organically
framework, POMs exhibit diverse potential applications in hybridized POMs display amphiphilic property in solutions
2
3
4
catalysis, biomedicine, photoelectric materials, and energy deriving from both hydrophilic and hydrophobic interactions,
materials,5 while the rich nanoscale morphology provides depending on the media to be dissolved.16
possibilities to serve as a building block for self-assemblies.6
As the chiral POMs are hard to synthesize based on their
However, in the case without assistant agents, the diversity and topologic structure meanwhile for those POMs possessing
7
stability of POMs’ assemblies are usually less controlled. To intrinsic chirality their asymmetry disappears quickly in aqueous
improve the capability in self-assembly, the polyanionic feature solution due to the dynamic exchange of oxygens in cluster with
of POMs has been used to combine with cationic organic those in water, it is a practicable approach to create chirality of
8
molecules through electrostatic interaction. The formed ionic POMs by induction of chiral countercations via ionic interaction
organic-inorganic complexes bring up amphiphilicity and while the cluster structure and other functional performance do
17
decrease the electrostatic repulsion, which direct to various self- not change. Following this idea, we herein would like to report
assembly structures accompanying by synergistic functions in our recent results by using simple counterions including
9
solutions, especially in organic media. One of the advantages in inorganic and organic cations to modulate the self-assemblies of
this route is that the complexes perform a whole unit whereas Anderson-type POMs that grafts a 1,3,5-triazine with two alkyl
each of the components plays independent role in the formed chains covalently in different solvent media. The
spherical/planar self-assembled structure and helical packing of
the POM as well as chiral amplification were built in solution
system, which are very important for further potential
State Key Laboratory of Supramolecular Structure and Materials, Institute of
Theoretical Chemistry and College of Chemistry, Jilin University, Changchun
1
30012, P. R. China
E-mail: libao@jlu.edu.cn
Electronic Supplementary
0.1039/x0xx00000x
applications in asymmetric catalysis in the ongoing studies.
The organically modified Anderson-type of POM were
prepared in two steps. The organic moiety of 1,3,5-triazine-
Information
(ESI)
available:
See
DOI:
1
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Page 2 of 5
COMMUNICATION
Journal Name
2
,4,6-triphenol grafting with two hexyl chains was firstly to line up in a wire like state. The transmissViieownArteiclleecOtnrloinne
synthesized via an etherization reaction. Then another microscopic (TEM) results show that the collapsed heres have
DOI: 10.1039sp/C9DT01780A
etherization of residue hydroxyl group with ethyl 2- a hollow structure with the size of 80 nm in diameter (Fig. 1b
bromoacetate was carried out following by an ester exchange and Fig. S14). With the addition of water, a transition from
reaction with tris(hydroxymethyl)methylamine via a modified spherical to fibrous assembly is observed at the volume ratio of
route of literatures.18 Finally, the organic part was linked to the CH
inorganic cluster through a one pot reaction, giving the final image shows layered substructure in the wire like assemblies
organically modified Anderson-type cluster (MnMo ) bearing (Fig. 1d and Fig. S15). When the volume ratio of water increases
(Scheme 1), to 4:1 (v/v), a sheet like assembly becomes dominant, and the
}3 discrete rectangle plates with rough surface have a scale of ca. 1
3 2
OH:H O (9:1, v/v) from SEM image (Fig. 1c). The TEM
6
tetrabutylammonium
(C N]
+{MnMo
cation
18[(OCH
(TBA)
[
−
4
H
)
9 4
3
6
O
)
2 3
2 43 3 3 2
CNHCH COC34H N O ]
(
abbrev. as TBA-MnMo
MnMo
), and (+)-bis[(R)-1-phenylethyl]ammonium (R-BPEA+) thickness is about 180 nm according to AFM result (Fig. S16).
and (‒)-bis[(S)-1-phenylethyl]ammonium (S-BPEA+) salts The detailed TEM image (Fig. 1f) by casting the sample onto a
abbrev. as R-MnMo and S-MnMo ), were prepared through an copper grid shows that the large planar assemblies consist of
ionic substitution reaction of TBA-MnMo following the small square like slices in a size of 30 nm, packing in a scaly
6
). The sodium salt (abbrev. as Na- um in width and ca. 2.5 um in length (Fig. 1e) while the average
6
(
6
6
6
published procedure.19 The synthetic route (Chart S1) and arrangement. The morphology change can be ascribed to the
detailed experiments were described in ESI and all intermediate polarity-induced increase of packing force driven by
and final products were encountered thorough purifications. The hydrophobic interaction of modified organic moiety. X-ray
resulting molecules were characterized by Elemental analysis diffraction of Na-MnMo
6
assemblies under different polar
1
(Table S1), H NMR, IR, and mass spectra (Fig. S1‒S13), which environments reveals a layered packing structure. Under pure
demonstrate the chemical compositions of the synthetic methanol solution, the observed layered packing has a thickness
molecules in full agreement with the target chemical structures. of ca. 2.49 nm (Fig. S17). With the addition of water to the ratio
The linear hybrid cluster shows amphiphilic feature due to the of CH OH:H O to 9:1 (v/v), two layered structures with
3 2
hydrophobicity of rigid-flexible organic moiety locating on both thickness of ca. 2.45 nm and 3.61 nm (Fig. S18) were found and
side of the disk like inorganic cluster and the hydrophilicity of at the ratio of 4:1 (v/v) only the layered structure with thickness
the polyanion. This property drives the hybrid cluster to organize of ca. 3.50 nm (Fig. S19) was detected. This means that the
into various self-assemblies in different environments. Though layered spacing also increases with the polarity increasing.
+
the prepared cluster complexes dissolve in many solvents, the
Na ion is hydrophilic and its size is small, which has little
detailed solubility still relies on the countercations used. To influence to the self-assembly of polyanionic part with the
avoid the influence of concentration on the morphology, the increase of polarity in solutions. When it is substituted with a
+
samples used in this work were all set as the same concentration cation TBA , which has a bigger size and an increased
(0.1 mg/mL) unless specially stated.
hydrophobicity, the ionic modulation to the assembly becomes
Scanning electron microscopic (SEM) results show that Na-
MnMo in pure methanol self-assembles into uniform spheres in
6
the large field of vision, as shown in Fig. 1a. Most of the spheres
are in a random dispersed state, while a small part of them tends
Scheme 1 Schematic drawing for the prepared hybrid cluster
Fig. 1 SEM and TEM images of Na-MnMo
6
in mixed solvent
with different cations, Na-MnMo
MnMo
6 6
, TBA-MnMo , and R-/S-
CH OH/H O (0.1 mg/mL) with the volume ratio of (a) and (b)
3
2
6
.
10:0, (c) and (d) 9:1, (e) and (f) 4:1, respectively, at 20 °C.
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
COMMUNICATION
more evident. For a pure methanol and CH
solvent with volume ratio of water of 17:3, the observed main
morphology is still spherical with the diameter from 50 nm to cluster estimated from the ideal molecular conformation is ca.
3
OH/H
2
O mixed is larger than that in weak polar solvents.
View Article Online
The full length of the organically mod d Anderson- pe
DOifI:ie10.1039/C9DT017ty80A
120 nm (Fig. 2a). With the increase of volume ratio of water to 5.1 nm. Because the polar head locates at the middle of the
4:1, these spheres tend to arrange into linear aggregation (Fig. amphiphilic molecule, it is hard to make it pack in a linear form
2b). When the water ratio increases to ca. 7:3, we can see clearly within a layered structure in polar media due to the hydrophobic
that the spheres fuse into belt like nanowire with the width about ends. However, considering the flexible bond at the amide bond
0 nm and length in several microns (Fig. 2c). At this state, there position, a folding can direct the head-tail separation structure,
5
are still some isolated spheres dispersing in the solution and where the hydrophilic cluster locates at one side while the
some spheres that do not fuse together completely attach on the hydrophobic alkyl chains locate the other side (Scheme 1). With
nanowires. Similar to that of Na-MnMo
6
, high resolution TEM this folding molecular conformation at a length ca. 2.5 nm, the
can assemble into interdigitated bilayer structure with
image of TBA-MnMo assemblies shows that the nanowires are MnMo
6
6
still in layered structure (Fig. 2d) with the distance of interlayer different overlapping from 2.18 nm to 2.5 nm, depending on the
ca. 2.4 nm, estimated from a statistic value on several images polarity of solvents. Apparently, the layered thicknesses are
+
(
Fig. S20−S21). In comparison to Na , due to the decreased often less than half of ideal length of Na-MnMo
6
and TBA-
+
polarity of TBA , TBA-MnMo
6
becomes soluble in weak polar MnMo
6
but they become reasonable when tilting and partial
solvents. With the addition of n-hexane into the mixed solution disorder of alky chains are considered (Scheme 2). It should be
of chloroform (3:2, in v/v), the formed assembly transfers from noticed that with the polarity increase, the layer thickness
sphere to regular sheet like morphology (Fig. 2e). Further becomes larger for Na-MnMo assembly. This can be ascribed
6
increasing the ratio of n-hexane leads to the size decrease with to the reduced interdigitation of hydrophobic part in a raised
rough edge (Fig. S22). However, TEM measurements polar environment due to the requirement for polyanionic head
demonstrate that regardless of the morphologic change, the exposing to the outside solution. In contrast, in reduced polarity
assemblies are always in a layered substructure with thickness of condition, the deep interdigitation allows the polyanionic head to
a bit more compact than that in aqueous solution (Fig. 2f). The hide in the bilayer region, leading to layer spacing getting
layer thickness in the increased polar solvent (CH
and 7:3 in v/v) is in the range of 2.51−2.41 nm, calculated from
XRD diffractions (Fig. S23−S24). But for the decreased polarity is substituted to R-/S- BPEA , the formed R-/S-MnMo
in mixture of CHCl
/n-hexane (1:1 v/v), the layer thickness apparent induced chirality. In contrast to the circular dichroism
becomes much thinner and reaches smallest to ca. 2.18 nm (Fig. signals of R-/S- BPEA alone emerging at the wavelength lower
S25). The results imply that the layer thickness in polar solvents than 250 nm, the Cotton signals of R-/S-MnMo appear at 275,
10, and 340 nm can be definitely ascribed to the induced
3
OH/H
2
O, 17:3 smaller.
When the counterion of the organically grafted MnMo
6
cluster
show
+
6
3
6
3
chirality of organic groups grafted on the cluster because of their
absorption at this region in UV-Visible spectra (Fig. 3a and Fig.
3b). As a comparison, the grafting ligand molecule in the mixture
with the chiral cations does not show induced activity of Cotton
signals. As there is no characteristic interaction between the
grafting group and the chiral cations, it can be concluded that it
is the electrostatic interaction drive the induced chirality in
organic phase. However, when R-/S-MnMo clusters dissolve in
6
chloroform solution, we do not observe chiral self-assemblies
and instead, straight plate like assembly becomes the main
Fig. 2 SEM images of TBA-MnMo
6 3 2
in CH OH/H O with the
volume ratio of (a) 17:3, (b) 4:1, (c) 7:3 and its corresponding (d) Scheme 2 Proposed packing model for simplified bilayer
TEM image; (e) SEM image of TBA-MnMo
6
3 6
in CHCl /n-C H
14 assembly structures of hybrid MnMo cluster with different
6
(3:2 in v/v) and its corresponding (f) TEM image. The cations versus the solvent polarity changes.
concentration is 0.1 mg/mL, and the temperature is 20 °C.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Page 4 of 5
COMMUNICATION
Journal Name
With the change of countercations with differVeienwtArstiiczleeOanlninde
DOI: 10.1039/C9DT017ty80A
asymmetric feature, an organically-modified Anderson- pe
POM bearing conjugate groups connecting alkyl chains
performed morphologic evolution from sphere to nanowire, plate,
and helical assemblies, with the modulation of solution polarity
from polar to non-polar change. The morphologic
transformations can be concluded to be dominated by the
assembly structure under different environments. More
importantly, the chirality deriving from organic countercations
can not only be transferred into inorganic cluster but also
amplified in the formed helical assemblies, which are not dealt
with before in POM related systems. In addition to the effect of
solvents, such chirality transfer and amplification could be very
important for chiral applications of POMs such as asymmetric
catalysis and chiral luminescence because in principle, the
present strategy does not require especial structural modification,
which may limit the properties of functional POMs.
6 6
Fig. 3 (a) UV-Vis spectra of TBA-MnMo , S-MnMo , and S-
BPEA∙Cl in CH
of R-MnMo , S-MnMo
CHCl /n-C 14 with different volume ratio (0.1 mg/mL) at 20°C,
and TEM images of (c) R-MnMo and (d) S-MnMo in CHCl /n-
14 (9:1 in v/v).
3
OH (0.1 mg/mL), (b) circular dichroism spectra
6
6
and their racemic mixture in solvent
3
6
H
Conflicts of interest
6
6
3
C
6
H
There are no conflicts to declare.
morphology (Fig. S26). This is quite similar to the assemblies
comprising of POMs covering with the same chiral cations in the Acknowledgements
literature20 and can be explained as lacking strong control of the
The authors acknowledge the financial supports received from
the National Natural Science Foundation of China (21773090,
1574057), the Changbaishan Distinguished Professor Funding
of Jilin Province, and the Program for JLU Science and
Technology Innovative Research Team (2017TD-10), Project of
Educational Commission of Jilin Province of China
binding force in the solvent.20 Interestingly, with the addition of
n-hexane, beside those induced Cotton signals, the enhancement
of signal intensity is also observed under the same concentration
as that in chloroform. An increased signal is detected with the
increase of n-hexane fraction up to 10%, which indicates the
effect of chirality amplification in the self-assemblies. Both SEM
and AFM characterizations provide the helical morphologic
images on the asymmetric self-assembly of chiral cation
2
(JJKH20190116KJ).
6
combined MnMo complexes (Fig. S27−28). Further TEM
Notes and references
measurement not only demonstrates the helical assembly
structure but also points out the layered packing of the hybrid
cluster complexes in asymmetrically twisted state (Fig. 3c−3d).
1
M. T. Pope and A. Müller, Angew. Chem. Int. Ed. Engl., 1991,
0, 34−38; P. T. Ma, F. Hu, J. P. Wang and J. Y. Niu, Coord.
3
Chem. Rev., 2019, 378, 281−309.
Different from the self-assembly of Na-MnMo
6
and TBA-
in polar solvents, the XRD results show that R-/S-
complexes possess a bigger layer thickness at ca. 3.9 nm
2
3
4
5
S. S. Wang and G. Y. Yang, Chem. Rev., 2015, 115,
MnMo
MnMo
6
4
893−4962.
Y. Tao, M. Q. Li, J. S. Ren and X. G. Qu, Chem. Soc. Rev.,
015, 44, 8636−8663.
B. Wang, L. H. Bi and L. X. Wu, J. Mater. Chem., 2011, 21,
9−71.
6
(Fig. S29). As this layer spacing value is much larger than the
2
folding state (ca. 2.5 nm) of the complex, the complete
interdigitation becomes no longer suitable to explain the packing
structure. Although the complex could adopt a tilted packing in
a full spreading form, the over interdigitation (Scheme 2) is more
likely due to the original interdigitated state of the racemic
mixture in chloroform solution, based on the thickness value of
ca. 2.7 nm (Fig. S30). In comparison to that chloroform is soluble
6
Y. Zhang, L. L. Wu, X. Y. Zhao, Y. N. Zhao, H. Q. Tan, X.
Zhao, Y. Y. Ma, Z. Zhao, S. Y. Song, Y. H. Wang and Y. G.
Li, Adv. Energy Mater., 2018, 1801139.
6
J. C. Luo, K. Chen, P. C. Yin, T. Li, G. Wan, J. Zhang, S. T.
Ye, Y. G. Wei and T. B. Liu, Angew. Chem. Int. Ed., 2018, 57,
for both hydrophobic and hydrophilic parts of R-/S-MnMo
6
4
067−4072; C. Falaise, M. A. Moussawi, S. Floquet, P. A.
complexes, the addition of n-hexane provides an incompatible
environment, which drives the hydrophilic cluster moiety to be
in tight packing while hiding itself inside of the layered structure
to reduce the interfacial energy.
Abramov, M. N. Sokolov, M. Haouas and E. Cadot, J. Am.
Chem. Soc., 2018, 140, 11198−11201.
S. Biswas, S. Vinnakota and S. Roy, RSC Adv., 2016, 6,
7
8
7
933−7940.
C. Venturello, E. Alneri and M. J. Ricci, Org. Chem., 1983, 48,
831−3833.
3
Conclusions
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
COMMUNICATION
9
H. L. Li, H. Sun, W. Qi, M. Xu and L. X. Wu, Angew. Chem.,
View Article Online
Int. Ed., 2007, 46, 1300−1303; W. F. Bu, L. X. Wu, X. Zhang
and A. C. Tang, J. Phys. Chem., B, 2003, 107, 13425−13431.
0 S. M. Zhang, Y. M. Zheng, S. Y. Yin, J. Z. Sun, B. Li and L.
X. Wu, Chem. Eur. J., 2017, 23, 2802−2810.
DOI: 10.1039/C9DT01780A
1
1
1
1 N. Noguchi, C. Chikara, K. Kuroiwa, K. Kaneko and N.
Kimizuka, Chem. Commum., 2011, 47, 6455−6457.
2 J. Zhang, W. Li, C. Wu, B. Li, J. Zhang and L. X. Wu, Chem.
Eur. J., 2013, 19, 8129−8135; J. Zhang, X. F. Chen, W. Li, B.
Li and L. X. Wu, Langmuir, 2017, 33, 12750−12758; B. Zhang,
W. M. Guan, F. F. Yin, J. X. Wang, B. Li and L. X. Wu, Dalton
Trans., 2018, 47, 1388−1392.
13 B. Hasenknopf, K. Micoine, E. Lacôte, S. Thorimbert, M.
Malacria and R. Thouvenot, Eur. J. Inorg. Chem., 2008,
5001−5013.
14 S. Landsmann, C. Lizandara-Pueyo and S. Polarz, J. Am.
Chem. Soc., 2010, 132, 5315−5321.
1
5 B. Hasenknopf, R. Delmont, P. Herson and P. Gouzerh, Eur.
J. Inorg. Chem., 2002, 1081−108; J. Zhang, Y. Long, W. M.
Xuan, C. G. Lin and Y. F. Song, Chin. Sci. Bull., 2017, 62,
685−692; J. W. Zhang, Z. L. Zhao, J. Zhang, S. She, Y. C.
Huang and Y. G. Wei, Dalton Trans., 2014, 43, 17296−17302;
J. W. Zhang, Y. C. Huang, G. Li and Y. G. Wei, Coord. Chem.
Rev. 2019, 378, 395−414.
16 B. Li, W. Li, H. L. Li and L. X. Wu, Acc. Chem. Res., 2017,
50, 1391−1399; X. L. Wang, Y. L. Wang, W. K. Miao, M. B.
Hu, J. Tang, W. Yu, Z. Y. Hou, P. Zheng and W. Wang,
Langmuir, 2013, 29, 6537−6545.
1
1
7 X. K. Fang, T. M. Anderson and C. L. Hill, Angew. Chem., Int.
Ed., 2005, 44, 3540−3544.
8 Y. Yan, H. B. Wang, B. Li, G. F. Hou, Z. D. Yin, L. X. Wu
and Y. W. W. Yam, Angew. Chem. Int. Ed., 2010, 49,
9233−9236; Y. Yan, B. Zhang, B. Li and L. X. Wu, Acta
Polym. Sin., 2017, 101−111.
1
9 Y. Yang, Y. Z. Wang, H. L. Li, W. Li and L. X. Wu, Chem.
Eur. J., 2010, 16, 8062−8071; Qi, W.; Li, H. L.; Wu, L. X., J.
Phys. Chem. B, 2008, 112, 8257−8263.
20 Y. Z. Wang, L. Shi, Y. Yang, B. Li and L. X. Wu, Dalton
Trans., 2014, 43, 13178−13186.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins