Supramolecular porous ionic network based on triazinonide and imidazolium: A template-free synthesis of meso-/macroporous organic materials: Via a one-pot reaction-assembly procedure

Article abstract of DOI:10.1039/c6ra20590a

A supramolecular porous ionic network (SPIN-1) was designed and prepared using a one-pot procedure, involving the quaternization of triimidazole triazine with cyanuric chloride followed by hydrolysis and in situ assembly. The structure of SPIN-1 was characterized by FT-IR, solid-state ¹³C CP/TOSS NMR, elemental analysis and XPS. SPIN-1 shows a BET surface area up to 263 m² g^-1 (average pore size 11 nm), and a CO₂ capture capacity of 24.7 cm³ g^-1, which is competitive for Carbon Capture and Storage (CCS).

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Supramolecular Porous Ionic Networkbased on Triazinonide and
Imidazolium: A Template-FreeSynthesis of Meso-/Macroporous
Organic Materials via One-Pot Reaction-Assembly Procedure
Received 00th January 20xx,
Accepted 00th January 20xx
Ze-HuanHeia, Gan-Lin Songa, Chen-Yu Zhaoa, WenhaoFanb, Mu-Hua Huanga*
DOI: 10.1039/x0xx00000x
A supramolecular porous ionic network (SPIN-1) was designed and prepared by one-pot procedure, involving the
quaternization of triimidazole triazine with cyanuric chloride followed by hydrolysis and in-situ assembly. The structure of
SPIN-1 was characterized by FT-IR, solid-state 13C CP/TOSS NMR,elemental analysis and XPS. SPIN-1 shows BET surface area
up to 263 m2/g (average pore size 11 nm), and a CO2 capture capacity of 24.7 cm3/g, which is competitive for Carbon
Capture and Storage (CCS).
www.rsc.org/
O
B
B
N
N
N
N
Introduction
O
O
B
N
N
N
N
N
N
Cl
Porous organic polymers (POPs) linked by covalent bond have
N
N
Cl
attracted much attention, since they shown widespread
11
Cl
=
N
Cl
N
N
N
Cl
applicationsin adsorption1ꢀ5,catalysis6ꢀ9
,
luminescence10,
,
N
N
N
Cl
N
N
N
O
B
O
B
batteries12, 13 and so on14, 15. Among them, Ionic porous organic
polymers16, 17 combine the unique featuresof ionic compounds
with the common properties of porous materials. Based on the
charges involved in the backbone of porous polymers, the ionic
porous organic polymers can be divided into cationic and
anionic type. Cationic type porous organic materials usually
contain positive charge in the backbone, such as ammonium18,
pyridinium19, imidazolium20, phosponium21 and so on. Based
on the covalent triazine frameworks (CTF)22, the imidazolium
CTF (Figure 1) was developed by Dai group20 for ion exchange.
A pyridium-based porous polymer named PAF-50 (Figure 1)
was designed and synthesized by Zhu group15. Correspondingly,
Anionic type porous organic materials usually contain negative
charge in the backbone, such as boronate.Tetraphenylborate
network was made by Long group for single ion conductor,
whose ionic conductivity reached 10-3 S/cm13. As far as
synthetic methods are concerned,the charged backbone in the
porous organic materials were are usually constructed through
covalent bond formation, i.e., the polymerization on the
charged monomer. In addition to covalent bond formation, a
supramolecular interaction was introduced to construct the
charged porous organic materials. For example, a novel
supramolecular organic frameworks (SOFs) by self-assembly of
cucurbit[8]uril and multi-armed pyridiniums were developed23ꢀ
B
Li
Cl
=
B
B
B
B
N
O
O
N
O
O
N
N
PAF-50 by Zhu group
Tetraarylborate network by Long group
Ionic CTF by Dai group
(CH2)
(CH2)
5
5
Cl
O
N
N
(CH2
)
P
(CH2
)
P
(CH2)
5
Cl
N
N
5
10
N
N
N
N
N
N
(H2C)5
OOC
(CH2)
5
N
N
O
n
N
O
N
N
N
NH
N
N
n
O
OOC
N
N
N
N
N
O
N
N
COO
N
N
N
O
N
Cl
COO
N
COO
CN
PILC by Yuan group
N
Supramolecular Ionic Network
by Grinstaff group
SPIN-1 in this work
Cl
Figure 1 Structure of some representative ionic porous organic
materials, supramolecular ionic networks and SPIN-1
Actually, the ionic bonds as the reversible non-covalent links was
first used by Grinstaff26, 27 group to construct the supramolecular
ionic networks (Figure 1) by combining multicationic and
multianionic compounds. And it was further developed by
Mecerreyeset. al.28,
, though the porous property was not
29
investigated in those work. Hierarchical organic porous materials30,
31
have enhanced properties such as good pore volume, large
accessible space and interconnected hierarchical porosity. By
polymeric multications and multianions,
a micro/mesoporous
polymeric ionic liquid complex (PILC)32 (Figure 1) can be prepared,
possibly owing to the relatively less flexible polymer chain
compared to small molecules. Mesoporous structures are especially
desirablein heterocatalysisbecause they are favorable to the mass
transfer of reactants6. The synthesis of the mesoporous POPs
usually requires templates such as SiO233and surfactants34,which
add troubles to remove templates. A template-free synthesis thus
attracted attention recently. Hazo-POPs were reported by Liu
group35 and divinylbenzene-based mesoporous POPs were
developed by Xiao group36 without using template. Hence, we
25
.
aSchool of Materials Science and Engineering, Beijing Institute of Technology,
Beijing, 100081, China. E-mail: mhhuang@bit.edu.cn
bBeijingCenter for Physical & Chemical Analysis, Beijing, 100089, China
Electronic Supplementary Information (ESI) available: additional figures See
DOI: 10.1039/x0xx00000x
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became interested in the template-free synthesis of porous organic solvent to dissolve the as-prepared SPIN-1.As
polymers based on supramolecular ionic network. controlexperiment, the solid obtained from mixing and
a
1
2
was
We wonder if the further introduction of rigid element to the collected by filtration, butwithout the hydrolysis and assembly
supramolecular ionic network will help the construction of process (Entry 5, Table 1). Indeed, the SPIN-1-5 was measured
porosity of the materials, e.g. an alternative anion and cation to have surface area as low as40 m2/g.
in the conjugated system plus πꢀπstacking37. Thetrisubstituted
a)
Adsorption
Desorption
3.0
b)
triazine with imidazolium38was reported to hydrolyze to give
structures with some of their counter ion delocalized to form
less charged conjugated structure39. Thus, the structure of
SPIN-1 (Figure 1) came into our mind.In this paper, we would
like to present the synthesis of SPIN-1 as a porous organic
material, makinguse of the hydrolysis of multi-armed
triazinewith imidazoliumfollowed by assembly of the ionic
segments.
2.5
2.0
1.5
1.0
0.5
0.0
400
200
0
0.0
0.2
0.4
0.6
P/P0
0.8
1.0
0
50
100
150
200
Pore Width (nm)
Figure 2, a) Adsorption (filled symbols) and desorption (empty
symbols)N2 isotherm of SPIN-1-2 at 77 K;b) Pore sizedistribution
curve by DFT
Results and discussion
In order to construct SPIN-1, we first synthesized 2,4,6-tri(1H-
The isothermof SPIN-1-2 with BET surface of 263m2/g was shown in
Figure 2. The increase in the nitrogen sorption at a high relative
pressure above 0.8 as well as a hysteresis loop at a high relative
pressure (0.6﹤P/P0﹤1.0) indicated a meso/macroporosity. Pore
distribution calculated by DFT (Figure 2) revealed an average pore
size of 11 nm. BJH calculation shows 1.4% of them are micropores,
77% of them are mesopores, and 21% of them are macropores
(Figure S4).Although SPIN-1 has a wide pore size distribution (Figure
2b), all samples prepared (Table S1) showed their pore volumes
increased along the surface area.
imidazol-1-yl)-1,3,5-triazine (
grams scale by modifying a reported procedure40, 41. The
structure
was characterized by FT-IR (Figure 3) and1H-NMR
2, Scheme 1) in 71% yield and
2
(FigureS1). The adsorption peaks at 3143 and 3113 cm-1
indicated the presence of unsaturated C-H bond, i.e. from
imidazole.Three peaks at 7.25,8.34and9.08ppm in 1H-NMR
revealed the presence of only one kind of imidazole ring. The
existence of
2 was confirmed by HR-ESI-MS (Figure S2) based
on [M+H]+ peak at 280.1052, which was required to be
280.1014. The above results were further supported by its
elemental analysis, showing C51.63%, H3.12%, N44.95% (Table
S2). The efforts to make SPIN-1 initiated by mixing cyanuric
With the sample of SPIN-1 with high BET surface area (Entry 2 of
Table 1), structure characterizations on it were carried out based on
FT-IR, solid NMR, elemental analysis (EA), X-ray photoelectron
spectra (XPS) and so on. The comparison between the IR spectra of
2 and SPIN-1 was shown in Figure 3. The absorption peak at 3115
cm-1in compound 2 (C-H of imidazole ring)has moved to higher
wavenumbers in SPIN-1, indicating the formation of charged
imidazole rings. The skeleton absorption at 810 cm-1 moved to
lower wavenumbers in SPIN-1, indicating that the triazine rings
were in negatively charged state (Scheme 1).
chlorideand compound
2 at room temperature and in
acetonitrile, which led to orange participation immediately.
Considering the hydrolysis of positively charged triazine will
release negative/positive charges and help the assembly via
electrostatic interaction, we stir the reaction mixture in
water/actonitrile for 2 h. To our delight, the sample of SPIN-1-
1 gave the Brunauer–Emmett–Teller (BET) surface area of 109
m2/g (Entry 1, Table 1). By lowering the concentration of 2
from 50 wt% to 1.5 wt%, the BET surface area increased to
more than 263m2/g (Entry 2, Table 1), with the increase of
pore volume from 0.37 to 0.75m3/g. However, the efforts to
increase either the assembly temperature or drying
temperature lead to lower BET surface (Entry 3 and 4, Table 1).
This shows the mild condition is suitable for the preparation of
SPIN-1 with high BET surface.
95
90
85
80
75
70
65
1706 cm-1
60
Table 1Optimization of conditions for preparing SPIN-1
55
50
45
40
35
30
Entry
Conc. of 2 (wt%)
Assembly temp.a
Dryingtemp.b
SAC /m2g-1
109
1
2
3
50
1.5
1.5
r.t.
r.t.
r.t.
r.t.
r.t.
263
152
85℃
r.t.
4
5
1.5
1.5
154
40
90 ℃
NAd
r.t.
4000
3000
2000
1000
aThe temperature for stirring the mixture with H2O beforefiltration. bThe temperature to remove
residual solvent from the materials. C The BET surface area.dNo assembly process was involed..
Figure 3, FT-IR spectra of 2 (blue) and SPIN-1 (red)
The use of solvents is reported to becrucial to makeporous
polymerised ionic liquids32.In our case, The role of water here
is surely to help hydrolysis of positively-charged triazine. In
addition, it acts as good solvent for the assembly and poor
The absorption peaks for both SPIN-1 and compound 2 in the range
of 1300-1600 cm-1 as well as 793-810 cm-1are super similar,
implying the main skeleton of imidazole andtriazine remained
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unchanged. The absorption peaks at 1706 cm-1 in the FT-IR
spectraof SPIN-1 (Figure 3, red line) indicated the presence of
The structure of SPIN-1 was further characterized by X-ray
photoelectron spectra (XPS, Figure 5). Consistent with the result
carbonyl group, which did not exist in compound 2 (Figure 3, blue concluded from FT-IR, only a part of Triazine rings were hydrolysed
line).However, this peak was very weak compared with peaks in the
range of 1300-1500 cm-1, meaning the extent of carbonyl group is
low, probably the phenol form is more favoured (Scheme 1). This
comparison revealed clearly that the carbonyl group in SPIN-1
resulted from the hydrolysis of a triazine imidazolium intermediates.
Beside FT-IR, the existence of triazine and imidazole subunit in
SPIN-1 was characterized by CP TOSS 13C-NMRand was compared
with 13C-NMR of compound 2as shown in Figure 4.
to give triazine-one (nitrogen at BE=400.8 eV and oxygen at 531.5
eV) by XPS. Peaks at 400.8, 399.7 and 398.3 eV were assigned to be
nitrogen atoms in hydrolysed triazine rings, imidazole rings and
neutraltriazine rings, respectively. The nitrogens didn’t perform
typical binding energy of ionic imidazole42 and triazines43, which
could be due to the counter ions linked directed to each other. It is
also observed that the reaction between 1 and 3 followed by
hydrolysis-assembly gave a quite acidic mixture (pH=1), which
provided white precipitates when treated with silver nitrate. This
must come from HCl byhydrolysis of C-Cl bond in substituted
chlorotriazine. However, after being washed twice by water, the
lotion was neutral. Through washing, most free chloridesin SPIN-
1are gone,only small parts remained in the materials (200.0 and
201.7 eV).This could be the indirect evidence for the mainchain
alternative ionic structure.
Based on the above observation, a possible chemical structure of
SPIN-1 and assumed mechanism was shown in Scheme 1.
Cl
N
Cl
N
N
N
N
N
N
N
N
N
N
Cl Cl
N
N
Cl
N
N
N
Cl
N
Cl
N
N
N
N
N
1
N
1
N
N
N
N
N
Cl
Cl
N
N
N
N
N
Cl
N
Cl
Cl
Cl
N
N
ACN
N
ACN
N
N
N
3
2
Figure 4,13C-NMR of 2(red) and CP TOSS 13C-NMR ofSPIN-1 (blue)
N
N
Cl
4
Cl
H2
O
N
ꢀHCl
The peaks for the carbon of triazine in 13C-NMR should appear at
around 160 ppm as is detected in compound 2. However, four peaks
were seen in the CP TOSS 13C-NMR in the range of 150-170 ppm,
indicating the original neutral triazine ring was both activated as
positively charged and deactivated as negatively charged. And the
carbon of the carbonyl group resulted from hydrolysis of
chlorotriazine shows the peak overlapped in this area. Similarly, the
imidazole subunit shows several peaks in the range of 100-140 ppm,
revealing neutral and positively charged imidazolium coexist in
SPIN-1. The alternative triazononide and imidazolium conjugated
structure was further supported by carefully comparing 13C-NMR of
O
N
N
H2
O
NH
N
O
N
Cl
HN
N
N
N
N
N
N
Cl
N
N
OH
N
N
O
N
Cl
N
O
HO
N
N
N
N
5
Cl
N
Cl
N
N
N
N
N
N
N
N
N
+
N
Cl
N
OH
N
N
Cl
O
Cl
7a
N
N
O
N
N
N
N
N
HCl
N
N
N
N
O
N
N
O
+
N
Cl
O
Cl
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
O
N
N
N
N
Cl
O
H
O
7b
SPIN-1
Cl
H
6
Scheme 1Possible structure and formation mechanism of SPIN-1
In acetonitrile, triimidazoletriazine2 reacted with cyacuric chloride 1
at room temperature to give imidazolium 3 and 4. The positively
chargedtriazineringin 3 and 4became highly reactive and some of
them could be hydrolyzed in the presence of water readily.For
example, 3 could be hydrolyzed to give 5 and 6. 4 could be
hydrolyzed to afford 7a, which could isomerize to 7b easily. These
hydrolyzed chemicalswith charges could assembly through
electrostatic interaction (or ionic complexation) as well asπꢀπ
stacking to form the SPIN-1. These intermolecular interactions
promote the formation of ionic cross-linking structure,which is non-
equilibrium. This process force their chain conformation fixed to
some extent. And this conformation fixation by ionic cross-linking is
one of the reasons to create porosity.Once the supramolecular ionic
network was formed, it precipitated as nanoparticles from
water/acetonitrile phase owing to poorer solubility. And the
nanoparticles further aggregate through supramolecular interaction
to the final product of SPIN-1.
SPIN-1 with triazinonidebridgedbisimidazolium salt37
.
N
O
C
Cl
d )10000
c) 22000
8000
20000
6000
18000
16000
-
4000
Cl
14000
12000
2000
10000
8000
520
0
525
530
535
540
545
Binding Energy (eV)
208
206
204
202
200
198
196
194
192
190
B.E.(eV)
Figure 5,XPS data of SPIN-1: a) Survey; b)N1s (up); c ) O1s; d) Cl2p
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The morphology of SPIN-1 was observed by Scanning Electron assembly procedure could happen in a short time which make it
Microscopy (SEM) and Transmission Electron Microscopy (TEM) hard to form ordered structure. It can be speculated that SPIN-1
(Figure 6).
formed its pores by a network at larger scale, in which the building
units were not molecules or segments but molecular clusters linked
by
supramolecular
interactions.
SPIN-1
has
a
hierarchicalmeso/macroporosity like some composite materials,
which is uncommon for typical porous organic polymers.
Climate change has become one major threat to the global
ecosystem and human society. Carbon capture and storage (CCS)
technology44 has been concerned to hold great promise as an
alternative solution, and a variety of advanced porous materials45
have been developed for their potential application in CCS. As a
new kind of charged porous organic polymers, Poly ionic liquids
(PILs) have shown promising carbon dioxide capture capacity46
.
Considering its ionic character similar to PILs,we investigated SPIN-1
toward CO2 capture capacity, whichwas measured by isotherm at
273 K (Figure 7).
25
Adsorption
Desorption
20
15
10
5
0
100 200 300 400 500 600 700 800
Absolute Pressure (mmHg)
Figure 7, CO2 isotherm for SPIN-1 at 273 K
It is up to 24.7 cm3/g at 1 bar and 273 K, which is high among all
PILs47. While some of PILs shows open adsorption-desorption cycle,
the adsorption of CO2 in SPIN-1 is reversible. The heat of adsorption
of SPIN-1 was measured to be 22.4 kJ/mol, which is also an
evidence of physical adsorption (much less than PILs, up to 40
kJ/mol). The interaction between CO2 molecules and SPIN-1 surface
was not as strong as PILs, which could be a result of less activated
imidazole ions that are not likely to form carbene. However, the
combination of basic nitrogen sites and polar surface could still be
effective, making SPIN-1 more suitable for CCS rather than chemical
fixation.
Figure 6, Typical images of SPIN-1: a) SEM of SPIN-1-5; b) SEM of SPIN-1-2; c)
TEM of SPIN-1-2
The SEM for the sample SPIN-1-5 (prepared from reaction between
compound
1
and
2
without hydrolysis and assembly
procedure)shows it had typical particle accumulation
morphology(Figure 6a).The irregular particles (1-2 μm) packed
closely to form irregular holes among them, leading to a poor
porosity.As a comparison, a network structure at nano-micrometre
scope with massive hollows(Figure 6b) was found in the
sample(SPIN-1-2)
by
in-situ
hydrolysis-assembly
procedure.Macropores scaled from tens of nanometres to several
micrometres could be observed directly, and the biggest pores were
beyond the measurement range of gas adsorption.Through TEM
image (Figure 6c), hierarchicalmesopores and macropores (shadows
over 50 nm) can be observed,agreeing with the result from nitrogen
sorption.It is clear to see from these pictures that SPIN-1 was a non-
crystalline material, which can also be found through powder X-ray
diffraction (PXRD) data (Figure S3). This could attribute to its fast
formation while water was added in. It indicates that the self-
Experimental
Materials
Imidazole and cyanuric chloride were purchased from Sinopharm
Chemical Regent Co. N,N-Diisopropylethylamine (DIPEA) was
purchased from Sigma Aldrich, tetrahydrofuran and acetonitrile
were purchased from Beijing Tongguang Fine Chemical Company.
All chemicals were used as received.
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Instrumentation
ARTICLE
Elemental analysis: C 38.89%，H 2.79%，N 35.44%.
Liquid 1H NMR spectra were recorded in DMSO-D6 on Varian
INOVA-400M magnetic resonance spectrometer. Solid-state NMR
experiments were performed on a Bruker WB Avance II 400 MHz
spectrometer. The 13C CP/MAS NMR spectra were recorded with a
4-mm double-resonance MAS probe and with a sample spinning
rate of 12.0 kHz. FT-IR spectra of the samples were collected on a
Nicolet 8700 Fourier transform spectrometer. The elemental
analysis of the polymer was determined using aElementarVario EL
Conclusions
In summary, a template-free, robust and cost effective strategy has
been developed to construct
a supramolecular porous ionic
network with alternative triazine and imidazole ions. The structure
of SPIN-1 was fully characterized, and the mechanism to form its
structure and porosity was proposed. Nitrogen sorption isothermal
exhibits that SPIN-1 processes BET surface area up to 263 m2/g,
with hierachicalmeso-/macroporosity. As a result of its ionic porous
surface, SPIN-1 has a carbon dioxide capture capacity up to 24.7
cm3/g, which is competitive among ionic porous organic polymers.
Further application of SPIN-1 on gas adsorption, catalysis and solid
conductor are under investigation.
CUBE analyzer. The surface areas were screened using
a
Micromeritics ASAP 2020 volumetric adsorption analyzer with a 9-
point BET measurement between the pressure range of 0.01-0.20
P/P0. Pore size distributions and pore volumes were derived from
the adsorption branches of the isotherms using the density
functional theory (DFT) pore model for pillared clay with cylindrical
pore geometry. Samples were degassed for 12 h under vacuum
before analysis. Carbon dioxide isotherms were measured at 273 K
and 298 K using a Micromeritics ASAP 2020 volumetric adsorption
analyzer. Field emission scanning electron microscopy (SEM)
observations were performed on a Hitachi S-4800 microscope
operated at an accelerating voltage of 10.0 kV. Transmission
electron microscopy (TEM) images were obtained with a Tecnai G2
F30. Transmission electron microscope operated at 300 kV.
Acknowledgements
The authors thank the National Natural Science Foundation of China
(No. 21202008) and Beijing Natural Science Foundation (No
2162039 ) for generous support.
Notes and references
Synthesis of 2,4,6-tri(1H-imidazol-1-yl)-1,3,5-triazine (2)
1. Q. Chen, M. Luo, P. Hammershoej, D. Zhou, Y. Han, B. W.
Laursen, C. Yan and B. Han, J. Am. Chem. Soc., 2012, 134, 6084-
6087.
2. X. Lu, D. Jin, S. Wei, Z. Wang, C. An and W. Guo, J. Mater. Chem.
A, 2015, 3, 12118-12132.
3. C. Pei, T. Ben and S. Qiu, Mater. Horiz., 2015, 2, 11-21.
4. S. S. Han, H. Furukawa, O. M. Yaghi and W. A. I. Goddard, J. Am.
Chem. Soc., 2008, 130, 11580-11581.
5. R. Dawson, A. I. Cooper and D. J. Adams, Prog. Polym. Sci., 2012,
37, 530-563.
To a solution of imidazole (5.45 g, 80mmol，5eq) and N,N-
Diisopropylethylamine (DIPEA) (30 mL，163 mmol，10 eq) in THF
(40 mL) was added a solution of 1 (3.0 g，16 mmol，1 eq) in THF
(40 mL) portionwise at room temperature The resulting mixture
was stirred at room temperature for another 1 h, and some pale
solid precipitated, which was washed by water followed by ethanol.
After being dried at 85 oC under vacuum, the title compound was
obtained as a white powder (3.2 g, yield 71%).
IR (KBr, cm-1):3143 (w), 3113 (w), 1572 (s), 1522 (m), 1448 (s), 1336
(m), 1303 (m), 1249 (s), 1194 (m), 1190 (m), 1057 (m), 996 (s), 895
(w), 850 (w), 810 (s), 794 (m), 743 (m), 648 (s), 607 (w), 558 (w).
1H NMR (400 MHz, DMSO-d6) δ (ppm): 7.25 (s, 3H),8.34 (s, 3H) ,
9.08 (s, 3H).
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13C NMR (400 MHz, DMSO-d6) δ (ppm): 117.6, 131.1, 137.7,162.1.
+
HR-MS (ESI): m/z 280.10522 [M+H]+ (found C12H10N9 , required
280.1014).
Elemental Analysis: C 51.63%, H 3.12%, N 44.95% (theoretical value
C 51.61%, H 3.25%, N 45.14%).
Synthesis of SPIN-1
To a solution of 2 (150 mg, 0.54 mmol，1 eq) in acetonitrile (100
mL) was added a solution of 1 (100 mg，0.54 mmol，1 eq) in
acetonitrile(5 mL). After stirred for 2.5 h, some orange solid was
formed. The reaction system was allowed to open and water (150
mL) was added in. The resulting mixture was stirred at room
temperature for another 2 h, and the solid became pale orange,
which was flittered out and washed by water followed by ethanol.
for three times separately. Drying at room temperature under
vacuum gave pale yellow powder of 70 mg.
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IR (KBr, cm-1):3137 (w), 1706 (w), 1550 (s), 1444 (s), 1341 (m), 1236
(m), 1174 (m), 1058 (w), 1003 (w), 881 (w), 849 (w), 801 (m).
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