The first route to highly stable crystalline microporous zirconium phosphonate metal-organic frameworks

Article abstract of DOI:10.1039/c4cc06223j

The first crystalline microporous zirconium phosphonate metal-organic framework (UPG-1) was synthesized using the novel tritopic ligand 2,4,6-tris(4-(phosphonomethyl)phenyl)-1,3,5-triazine. Its crystal structure was solved ab initio from laboratory powder X-ray diffraction data. UPG-1 displays remarkable thermal stability and hydrolysis resistance and has a good absorption affinity towards n-butane and CO₂. This journal is

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ARTICLE TYPE
The first route to highly stable crystalline microporous zirconium
phosphonate metal-organic frameworks
a
a
a
b
b
Marco Taddei, Ferdinando Costantino, Fabio Marmottini, Angiolina Comotti, Piero Sozzani, and
c
Riccardo Vivani*
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
The first crystalline microporous zirconium phosphonate
Metal-Organic Framework (UPG-1) was synthesized using
it emerges that the synthesis of microporous and crystalline Zr
phosphonate MOF has been a challenge to date.
the
novel
tritopic
ligand
(2,4,6-tris(4-
1
0
(phosphonomethyl)phenyl)-1,3,5-triazine. Its crystal structure
was solved ab initio from laboratory powder X-ray
diffraction data. UPG-1 displays remarkable thermal stability
and hydrolysis resistance and has a good absorption affinity
towards n-butane and CO2.
1
2
2
3
3
4
4
5
0
5
0
5
0
5
MetalꢀOrganic Frameworks (MOFs) based on Zirconium
(hereafter ZrꢀMOFs) are attracting a growing interest in the
scientific community due to their unique features in term of
enhanced robustness and stability towards high temperature and
5
0
Chart 1 Molecular structure of H
6
ttbmp, in comparison with that of
1
hydrolysis. As a matter of fact, as compared to the vast number
H
6
btbp.
of MOFs reported in the literature, MOFs containing Zr oxo
clusters as Secondary Building Units (SBUs) are much more
resistant to aggressive conditions and then useful for applications
In a recent paper, we used a tritopic phosphonic ligand with
zirconium, namely the 1,3,5ꢀtris(4ꢀphosphonophenyl)benzene
in which an enhanced stability is required, such as heterogeneous 55 (H
btbp), in order to prevent the formation of dense layered
motifs. The obtained compound (Zrbtbp) had an unprecedented
6
2
8
catalysis in oxidizing reagents, CO storage and separation from
2
3
industrial flue gases, and so on. The ZrꢀMOFs reported in the
honeycombꢀlike layered structure, featuring large cavities, but no
permanent porosity was detected. The lack of porosity was
attributed to the formation of zeroꢀdimensional (0D) inorganic
literature are based either on simple aromatic carboxylates, such
1
a,b
as terephtalic acid (UiOꢀ66 and MILꢀ140), or on more bulky
[
1c]
ligands like pyreneꢀ (NUꢀ1000)
and porphyrineꢀ 60 building units, which did not allow the expansion of the structure
1d,e,f
tetracarboxylates (PCNꢀ222, 224 and MOF 525, 545).
in the third dimension. Moreover, the layers stacked in such a
way that the cavities were capped, thus making them non
Phosphonate ligands are considered as good candidates for the
attainment of highly robust MOFs as well, despite their marked
tendency to yield extended dense structures. Indeed, only a few
accessible to N
only adopt a planar arrangement, which might induce the
further
improvement was then addressed to the synthesis of a similar
and CO . The btbp ligand is very rigid and can
2
2
examples of crystalline phosphonate based MOFs with permanent 65 formation of the layered structure of Zrbtbp.
A
microporosity were reported to date, mostly based on divalent or
4
trivalent metals.
tritopic ligand possessing a slightly higher conformational
freedom: the novel (2,4,6ꢀtris(4ꢀ(phosphonomethyl)phenyl)ꢀ
1,3,5ꢀtriazine (hereafter H ttbmp), whose structure is shown in
6
In this context, the preparation of zirconium phosphonate
MOFs with permanent porosity is an attractive goal that, in the
past, has been mainly pursued by combining small and large 70 Chart 1. To the best of our knowledge, this ligand was never used
5
ligands, in order to generate interlayer microporosity. However,
the obtained compounds suffered from scarce crystallinity and
stability. There are also some examples of microꢀ and mesoꢀ
porous zirconium phosphonates displaying absorption and
for the preparation of MOFs.
ttbmp and H btbp differ for two main features: the inner
core in H ttbmp is an sꢀtriazine instead of the benzene in H btbp,
simply because the precursor 4ꢀ(bromomethyl)benzonitrile is a
ttbmp
contains benzylphosphonic groups in place of phenylphosphonic
groups, in order to impart some flexibility to the molecule.
Details of the synthesis of H ttbmp are reported in the ESI: it was
H
6
6
6
6
separation properties, but none of them was obtained in 75 commercially available and cheap product; furthermore, H
6
microcrystalline form, therefore their structure was not
6
determined. On the other hand, a few crystalline openꢀ
framework zirconium phosphonates were reported, but they did
6
7
not display permanent porosity. From the above considerations,
carried out in three steps, each with a very good yield (96%, 95%,
and 85%, respectively).
80
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The synthesis of the ZrꢀMOF based on ttbmp (hereafter UPGꢀ1,
UPG = University of Perugia) was carried out in water/methanol
30
The open framework structure is based on the connection of
1D chains, composed of ZrO octahedra and PO C tetrahedra and
6
3
at 80 °C starting from ZrOCl and using hydrofluoric acid as a
extended along the cꢀaxis, via the ttbmp ligands. The zirconium
atom lies on an inversion center and it is coordinated by six
oxygen atoms belonging to six different phosphonate tetrahedra:
two of them are monodentate, whereas the remaining four are
bidentate, connecting zirconium atoms along the cꢀaxis, as shown
in Figure 3. Inorganic chains based on the same connectivity
were previously observed only in another 3D zirconium
2
3
4
4
5
5
6
6
5
0
5
0
5
0
5
9
phosphonate.
Each ttbmp ligand features three different phosphonate groups:
two of them are connected to the zirconium atoms as described
above, whereas the third is non coordinated and points toward the
ꢀ3 symmetry operator; it is worth to note that uncoordinated
5
Fig. 1 Final Rietveld and difference plot for UPGꢀ1.
phosphonate groups are rarely found in similar systems. The
ttbmp ligands are efficiently stacked along the cꢀaxis direction,
acting as bridges between adjacent inorganic chains. Two kinds
of channels with different sizes are formed in the structure: one
has a free diameter of about 10 Å, and it is lined by both free PꢀO
groups and aromatic rings; the other has a free diameter of about
5 Å and is lined only by the uncoordinated PO C groups (Figure
3
1
S). 10 water molecules per Zr atom are accommodated in these
channels and are involved in intricate hydrogen bond networks.
The use of the more flexible ttbmp ligand, if compared with
the previously reported btbp, allowed a crucial improvement to
the framework assembly process: as a matter of fact, the
possibility of the phosphonic tetrahedra to be outꢀofꢀplane with
respect to the aromatic internal core induced a different
connection to zirconium atoms thus overcoming the formation of
0
D SBU found in Zrꢀbtbp, which were stacked in an
Fig. 2 The crystal structure of UPGꢀ1 viewed along the cꢀaxis. ZrO
6
unfavourable way to form infinite channels. In UPGꢀ1 the
conformation of the ligand favoured the assembly of infinite 1D
CBUs running along the cꢀaxis and the hexagonal channels here
formed are accessible to gases.
The comparison of the PXRD patterns for the asꢀsynthesized
and the anhydrous compound suggests that the structure
undergoes small changes upon removal of water. This process is
fully reversible and the solvent can be reꢀadsorbed if the solid is
kept in hot water (Figure 2S). Unfortunately, the diffraction
pattern of the anhydrous compound shows a relevant loss of
70 crystallinity, not allowing a complete crystal structure refinement.
However, a full profile refinement procedure, performed with the
Le Bail method, on UPGꢀ1 outgassed at 160 °C for 24 h, that is
after the same treatment used before performing gas adsorption
measurements (Figure 3S), revealed that the crystal structure and
3
octahedra are represented in purple, coordinating PO C tetrahedra are in
green.
10
Fig. 3 The structure of the inorganic chains found in UPGꢀ1. ZrO
octahedra are represented in purple, PO C tetrahedra are in green.
Hydrogen bonds are represented as red dashed lines.
6
3
mineralizer (see ESI for details). UPGꢀ1 is a very insoluble
compound and it is obtained as a microcrystalline powder. Its
formula is Zr[H ttbmp] ⋅10H O. The crystal structure of UPGꢀ1
15
20
25
4
2
2
7
5
space group of the as synthesized compound were found to be
retained. The refined unit cell parameters [a = 59.071(2) Å, c =
was solved and refined by laboratory Powder XꢀRay Diffraction
(PXRD) data. It crystallizes in the trigonal space group R ꢀ3 and
5
.202(1) Å] show a very small change, and the volume of this
its lattice parameters are a = 60.674(2) Å, c = 5.1278(3) Å. Final
Rietveld and difference plot is shown in Figure 1 (see ESI for
crystallographic data and refinement details).
3
cell, 15720(3) Å , is about 4% smaller than that of the hydrated
compound, suggesting that the solid retains its crystalline
3
80 framework upon dehydration.
The cell volume of 16348 Å is by far the largest ever reported
13
C CP MAS NMR spectrum of UPGꢀ1 (Figure 5S) exhibits
for any zirconium phosphonate, and the calculated density of 1.25
ꢀ
3
the presence of the organic phosphonate ligand and a signal
multiplicity in agreement with the number of independent
carbons in the unit cell. No impurities are shown.
Field EmissionꢀScanning Electron Microscopy (FEꢀSEM)
images (Figure 6S) show the elongated morphology of the
microcrystals as prismatic rods with sizes ranging from 0.5 to 10
g cm matches that of the anhydrous form of Zrꢀbtbp as the
lowest ever observed. The calculated solvent accessible volume is
3
about 5367 Å , which represents the 32.8% of void volume. Hꢀ
8
5
atoms were omitted in the structural refinement but considered
for the void calculation. The structure of UPGꢀ1 is shown in
Figure 2.
2
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ꢁ
m, measured along the elongation axis. Some crystals clearly
favorably interact with aromatic rings of the host structure
...
show the hexagonal morphology of the terminal face of the 60 through CH π interactions. No hysteresis between adsorption and
prisms, thus suggesting that the crystal symmetry reflects that of
the ligand.
The permanent porosity of UPGꢀ1 was demonstrated by
adsorption isotherms of gases. The CO2 isotherm at 195 K,
3
desorption curves was found and, at P/P = 0.95, 48 cm STP/g of
0
adsorbed nꢀbutane was measured. Considering the density of the
3
5
liquid nꢀbutane at 273 K equal to 0.602 g/cm , the limit uptake
3
value of 0.2 cm /g can be estimated. Such value is in agreement
reported in Figure 4a, shows a Langmuir typeꢀI profile which 65 with that estimated from CO occupancy at saturation at 195K.
2
3
reaches the value of 112 cm /g (22 wt%) at 1 bar. The compound
exhibits BET and Langmuir surface areas of 410 m²/g and 514
1
1
2
2
3
3
4
4
5
5
0
5
0
5
0
5
0
5
0
5
m²/g, respectively, as calculated by using the relative pressure
3
range 0.02<P/P <0.15. Considering the empty space of 4450 Å
0
per unit cell, as explored by a probe sphere of 1.6 Å equal to the
kinetic radius of CO , and the maximum measured CO capacity
70
75
80
85
90
95
2
2
3
of 5 mmol/g, a CO density of 1.07 cm /g was calculated. This
2
value is in agreement with the density of CO in the liquid state
2
3
and enabled the estimation of 0.2 cm /g pore volume. This result
indicates the complete filling of both large and small channels (10
and 5 Å diameter) which are easily accessible to gas species via
diffusion. Considering the uptake values, the effectiveness of this
system exceeds that of microporous copperꢀphosphonate MOFs
4
f
recently published and is comparable with microporous
4
b
phosphonateꢀbased MOFs such as MILꢀ91(Ti), MILꢀ91(Al),
4
e
phosphonate monoesters with Zn(II), and the Zrꢀbased MOFs
MILꢀ140 A and MILꢀ140 B. N adsorption isotherm at 77 K
2
showed a negligible gas uptake probably due to the slow
4
e
adsorption kinetics at such low temperature. Contrarily, in the
case of CO the higher temperature of adsorption isotherm and
2
the quadrupole moment facilitated the penetration of gas
molecules into the cavities.
In order to investigate selective CO capture with respect to
2
other gases, we collected CO , CH , and N adsorption isotherms
2
4
2
of UPGꢀ1 under the mild temperature conditions of 273 and 298
K (Figure 4b). N adsorption isotherms up to 10 bar still show
2
low uptake values and the amount is proportional to the pressure
in the range up to 10 bar, indicating an extremely low nitrogen
affinity for the absorbent. Concerning CO , the maximum uptake
2
3
3
values were found to be 76 cm /g and 69 cm /g at 10 bar,
corresponding to 150 mg/g and 136 mg/g for CO , respectively.
2
The compound exhibits a good binding affinity for CO , as
2
shown by the isosteric heat of adsorption, Q , of 24 kJ/mol as
st
calculated by ClausiusꢀClapeyron equation, indicating the
formation of favourable interactions of CO with the aromatic 100
2
rings and the phosphonate groups lining the inner surface of the
9
pores. These results can be exploited favourably for selective
absorption of carbon dioxide in a mixture with nitrogen. The
selectivity of CO /N binary mixtures was determined from the
2
2
singleꢀcomponent isotherms using ideal adsorbed solution theory 105
1
0
(
IAST), which has been successfully employed to calculate gas
mixture separation by microporous materials. Under the mild
conditions of room temperature and low pressure, UPGꢀ1 shows
CO /N selectivity of 24, in a 15:85 CO /N binary mixture,
2
2
2
2
Fig. 4 Adsorption isotherms of porous UPGꢀ1 compound: a) CO
2
(red
which is representative of industrial operative conditions (Figure
S). Moreover, the UPGꢀ1 material is selective for CO2 with
circles) and CH (blue triangles) isotherms at 195 K and 1 bar, the
4
7
110
desorption isotherms are indicated by white circles and triangles,
respect to CH , highlighting the stronger affinity of the system to
respectively; b) CO , CH and N adsorption isotherms collected at 298 K
4
2
4
2
CO due to its quadrupolar nature.
(green labels) and 273 K (blue labels) and up to 10 bar. c) nꢀbutane
adsorption (filled circles) and desorption (void circles) isotherms at 273 K
on UPGꢀ1.
2
Interestingly, this system can efficiently adsorb hydrocarbons
such as nꢀbutane (Figure 4c). The slope at low partial pressure of
butane is very steep indicating that butane molecules can
1
15
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T. Nguyen, P. C. Stair, R. Q. Snurr, O. K. Farha and J. T. Hupp, J.
Am. Chem. Soc. 2013, 135, 10294ꢀ10297; (d) D. Feng, Z.ꢀY. Gu, J.ꢀ
R. Li, H.ꢀL. Jiang, Z. Wei and H.ꢀC. Zhou, Angew. Chem. Int. Ed.
6
6
0
5
UPGꢀ1
displays
a
remarkable
thermal
stability.
Thermogravimetric (TGA) and temperature dependent Xꢀray
diffraction (TDXD) analyses are reported in Figure 8S and 10S,
respectively. Based on the TDXD analysis, the compound is
stable up to about 430 °C. Between 350 and 400 °C the sample
2
012, 124, 10453ꢀ10456; (e) D. Feng, W.ꢀC. Chung, Z. Wei, Z.ꢀY.
Gu, H.ꢀL. Jiang, Y.ꢀP. Chen, D. J. Darensbourg and H.ꢀC. Zhou, J.
Am. Chem. Soc. 2013, 135, 17105ꢀ17110; (f) W. Morris, B.
Volosskiy, S. Demir, F. Gándara, P. L. McGrier, H. Furukawa, D.
Cascio, J. F. Stoddart and O. M. Yaghi, Inorg. Chem. 2012, 51, 6443ꢀ
5
0
5
0
undergoes
a phase transformation evidenced by a slight
6
445;
(a) L. Ma, C. Abney and W. Lin, Chem. Soc. Rev. 2009, 38, 1248ꢀ
256; (b) J. Lee, O. K. Farha, J. Roberts, K. Scheidt, S. T. Nguyen
displacement of the first two peaks which are moved towards
higher 2θ angles. This new phase is stable up to 430 °C and, after
that temperature, the framework collapses and the peaks relative
to the formation of zirconium pyrophosphate appear. The thermal
stability is then higher than the related Zrbtbp material previously
reported and comparable to other carboxylate based ZrꢀMOFs
like UiOꢀ66 and MILꢀ140.
2
1
1
1
2
70
75
and J. T. Hupp, Chem. Soc. Rev. 2009, 38, 1450ꢀ1459; (c) A.
Dhakshinamoorthy, M. Alvaro and H. Garcia, Catal. Sci. Technol.
2
011, 1, 856ꢀ867. (d) F. Vermoortele, R. Ameloot, A. Vimont, C.
Serre and D. De Vos, Chem. Commun. 2011, 47, 1521ꢀ1523. (e) J.
Chen, K. Li, L. Chen, R. Liu, X. Huang and D. Ye, Green Chem.
2014, 16, 2490ꢀ2499.
The stability towards hydrolysis was also investigated by
treating UPGꢀ1 in various conditions (see ESI for details). The
compound fully retained the crystallinity and the amount of the
solid recovered, after each treatment, was nearly the same than
the initial weight, indicating that no significant dissolution
occurred, whereas in the same conditions UiOꢀ66 underwent
partial hydrolysis (Figure 11S and 12S).
3
4
(a) D. M. D’Alessandro, B. Smit and J. R. Long, Angew. Chem. Int.
Ed. 2010, 49, 6058ꢀ6082. (b) Q. Yang, A. D. Wiersum, V. Guillerm,
C. Serre, P. L. Llewellyn and G. Maurin, J. Phys. Chem. C 2011, 66,
1
3768ꢀ13774. (c) G. E. Cmarik, M. Kim, S. M. Cohen and K. S.
8
8
0
5
Walton, Langmuir 2012, 28, 15606ꢀ15613.
(a) G. K. H. Shimizu, R. Vaidhyanathan and J. M. Taylor, Chem.
Soc. Rev. 2009, 38, 1430ꢀ1449; (b) C. Serre, J. A. Groves, P.
Lightfoot, A. M. Z. Slawin, P. A. Wright, N. Stock, T. Bein, M.
Haouas, F. Taulelle and G. Férey, Chem. Mater. 2006, 18, 1451–
1457; (c) J. A. Groves, S. R. Miller, S. J. Warrender, C. Mellotꢀ
Draznieks, P. Lightfoot and P. A. Wright, Chem. Commun. 2006,
Conclusions
3
305ꢀ3307; (d) M. T. Wharmby, J. P. S. Mowat, S. P. Thompson and
A novel ZrꢀMOF based on a phosphonate ligand is here
presented. To the best of our knowledge it represents the first
crystalline microporous MOF based on zirconium phosphonate.
In this work we found that, by using a tritopic phosphonic ligand
with a higher flexibility degree if compared with the previously
reported btbp ligand, it was possible to induce the formation of an
open framework structure with accessible channels. UPGꢀ1 has
P. A. Wright, J. Am. Chem. Soc. 2011, 133, 1266ꢀ1269; (e) S. S.
Iremonger, J. Liang, R. Vaidhyanathan and G. K. H. Shimizu, Chem.
Commun. 2011, 4430ꢀ4432; (f) M. Taddei, F. Costantino, A. Ienco,
A. Comotti, P. V. Dau and S. M. Cohen, Chem. Commun. 2013, 49,
2
3
3
4
5
0
5
0
90
95
00
05
10
15
1
315ꢀ1317; (g) M. Pramanik, A. K. Patra and A. Bhaumik, Dalton
Trans. 2013, 42, 5140ꢀ5149; (h) M. Pramanik and A. Bhaumik,
Chem. Eur. J. 2013, 19, 8507ꢀ8514; (i) S.ꢀF. Tang, J.ꢀJ. Cai, L.ꢀJ. Li,
X.ꢀX. Lv, C. Wang and X.ꢀB. Zhao, Dalton Trans. 2014, 43, 5970ꢀ
5
973.
permanent microporosity and good selectivity towards CO over
2
5
6
(a) G. Alberti, U. Costantino, F. Marmottini, R. Vivani and P.
Zappelli, Angew. Chem. Int. Ed. 1993, 32, 1357ꢀ1359; (b) G. Alberti,
R. Vivani, F. Marmottini and S. Murcia Mascaros, Angew. Chem. Int.
Ed. Engl. 1994, 33, 1594ꢀ1597.
(a) R. Vivani, F. Costantino, U. Costantino and M. Nocchetti, Inorg.
Chem. 2006, 45, 2388ꢀ2390; (b) M. Taddei, F. Costantino and R.
Vivani, Inorg. Chem., 2010, 49, 9664–9670.
M. Taddei, F. Costantino, R. Vivani, S. Sabatini, S.ꢀH. Lim and S. M.
Cohen, Chem. Commun. 2014, 50, 5737ꢀ5740.
M. Taddei, A. Donnadio, F. Costantino, R. Vivani and M. Casciola,
Inorg. Chem. 2013, 52, 12131–12139.
N , enhanced thermal stability and outstanding resistance to
2
hydrolysis. Future efforts will be addressed to the use of ligands
similar to ttbmp, in order to investigate the possibility to obtain
other microporous compounds and to perform isoreticular
syntheses.
The authors thank Dr. Andrea Ienco for TDXD measurements.
M. T., R. V., F. C., F. M. thank project “Fondazione Cassa di
Risparmio di Perugia ꢀ no. CRP2013021260”. A. C. thanks
projects “Fondazione Cariplo 2012ꢀ0921” and “MIUR ꢀ PRIN
2011”.
1
1
1
1
7
8
9
(a) P. Sozzani, S. Bracco, A. Comotti, L. Ferretti and R. Simonutti,
Angew. Chem. Int. Ed. 2005, 44, 1816ꢀ1820; (b) P. Sozzani, A.
Comotti, S. Bracco and G. Distefano, Chem. Commun. 2009, 284ꢀ
Notes and references
2
86; (c) A. Comotti, A. Fraccarollo, S. Bracco, M. Beretta, G.
Distefano, M. Cossi, L. Marchese, C. Riccardi and P. Sozzani,
CrystEngComm 2013, 15, 1503ꢀ1507.
a
Dipartimento di Chimica, Biologia e Biotecnologie, University of
Perugia, Via Elce di Sotto 8, 06123, Perugia, Italy
b
10 A. L. Myers and J. M. Prausnitz, Thermodynamics of mixedꢀgas
adsorption. AIChE J. 1965, 11, 121ꢀ127.
Dipartimento di Scienza dei Materiali, University of Milano Bicocca,
45
50
55
Via R. Cozzi 53, 20125, Milano, Italy
c
Dipartimento di Scienze Farmaceutiche, University of Perugia, Via del
Liceo 1, 06123, Perugia, Italy; Email: riccardo.vivani@unipg.it
†
Electronic
Supplementary
Information
(ESI)
available:
[
Crystallographic Information File (CIF) for UPGꢀ1 (CCDC: 1013734).
Refinement details. Additional figures. Experimental part.]. See
DOI: 10.1039/b000000x/
1
(a) J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S.
Bordiga and K. P. Lillerud, J. Am. Chem. Soc. 2008, 130, 13850ꢀ
1
3851. (b) V. Guillerm, F. Ragon, M. DanꢀHardi, T. Devic, M.
Vishnuvarthan, B. Campo, A. Vimont, G. Clet, Q. Yang, G. Maurin,
G. Férey, A. Vittadini, S. Gross and C. Serre, Angew. Chem. Int. Ed.
2
012, 51, 9267ꢀ9271; (c) J. E. Mondloch, W. Bury, D. Fairenꢀ
Jimenez, S. Kwon, E. J. DeMarco, M. H. Weston, A. A. Sarjeant, S.
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