Metal-organic framework based on a trinickel secondary building unit exhibiting gas-sorption hysteresis

Article abstract of DOI:10.1021/ic070338v

An interpenetrating microporous metal-organic framework based on a μ₃-oxotrinickel basic carboxylate secondary building unit has been synthesized and structurally characterized. It exhibits pronounced gas-sorption hysteresis and selective adsorption of carbon dioxide over methane.

Full text of DOI:10.1021/ic070338v

Inorg. Chem. 2007, 46, 3432−3434
Metal
−Organic Framework Based on a Trinickel Secondary Building Unit
Exhibiting Gas-Sorption Hysteresis
Shengqian Ma, Xi-Sen Wang, Erika S. Manis, Christopher D. Collier, and Hong-Cai Zhou*
Department of Chemistry & Biochemistry, Miami UniVersity, Oxford, Ohio 45056
Received February 21, 2007
An interpenetrating microporous metal
−
organic framework based
their application potential. Their amenability to design,8
exceptionally high surface area,9 and framework flexibility1b,10
set porous MOFs apart from traditional zeolites11 and
carbonaceous materials.12 Introduction of weak interactions
such as hydrogen bonding and π-π interaction into the
architecture of porous materials can not only improve the
framework flexibility but also induce interpenetration in
MOFs.1b,13 Although interpenetration is generally considered
to reduce the porosity,14 it can tune the pore size in MOFs
for their application in gas separation.15 For the above
reasons, MOFs based on weak interactions may be particu-
larly useful for selective gas adsorption. Herein, we report
an interpenetrating microporous nickel MOF, PCN-5 (PCN
represents a porous coordination network), exhibiting gas-
adsorption selectivity of carbon dioxide over methane and
pronounced gas-sorption hysteresis.
on a 3-oxotrinickel basic carboxylate secondary building unit has
µ
been synthesized and structurally characterized. It exhibits
pronounced gas-sorption hysteresis and selective adsorption of
carbon dioxide over methane.
Porous metal-organic frameworks (MOFs)1 have attracted
widespread interest in the past decade because of their
fascinating structures2 and intriguing potential applications.
Studies in catalysis,3 magnetism,4 nonlinear optics,5 separa-
tion,6 and gas storage7 illustrate the versatility of MOFs and
* To whom correspondence should be addressed. E-mail: zhouh@
muohio.edu.
(1) (a) Yaghi, O. M.; Li, H.; Davis, C.; Richardson, D.; Groy, T. L. Acc.
Chem. Res. 1998, 31, 474. (b) Kitagawa, S.; Kitaura, R.; Noro, S.-i.
Angew. Chem., Int. Ed. 2004, 43, 2334.
(2) (a) Delgado-Friedrichs, O.; O’Keeffe, M.; Yaghi, O. M. Acta Crys-
tallogr., Sect. A: Found. Crystallogr. 2003, 59, 515. (b) Batten, S. R.
J. Solid State Chem. 2005, 178, 2475. (c) Ockwig, N. W.; Delgado-
Friedrichs, O.; O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2005,
38, 176. (d) Ma, S.; Fillinger, J. A.; Ambrogio, M. W.; Zuo, J.-L.;
Zhou, H.-C. Inorg. Chem. Commun. 2007, 10, 220.
(3) (a) Seo, J. S.; Whang, D.; Lee, H.; Jun, S. I.; Oh, J.; Jeon, Y. J.; Kim,
K. Nature 2000, 404, 982. (b) Hu, A.; Ngo, H. L.; Lin, W. J. Am.
Chem. Soc. 2003, 125, 11490. (c) Zou, R.; Sakurai, H.; Xu, Q. Angew.
Chem., Int. Ed. 2006, 45, 2542.
A solvothermal reaction between Ni(NO3)2·6H2O and
H3TATB (TATB represents 4,4′,4′′-s-triazine-2,4,6-triyl-
tribenzoate) in dimethylformamide (DMF) using a Teflon-
lined autoclave afforded light-green crystals of PCN-5 (yield
50%) with an overall formula of H2[Ni3O(H2O)3(TATB)2]·
5DMF·2H2O, which was determined by X-ray crystal-
(8) (a) Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.;
O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319. (b) Yaghi,
O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.;
Kim, J. Nature 2003, 423, 705. (c) Fe´rey, G.; Mellot-Draznieks, C.;
Serre, C.; Millange, F. Acc. Chem. Res. 2005, 38, 217.
(4) (a) Halder, G. J.; Kepert, C. J.; Moubaraki, B.; Murray, K. S.; Cashion,
J. D. Science 2002, 298, 1762. (b) Janiak, C. J. Chem. Soc., Dalton
Trans. 2003, 2781. (c) Zheng, Y.-Z.; Tong, M.-L.; Zhang, W.-X.;
Chen, X.-M. Angew. Chem., Int. Ed. 2006, 45, 6310.
(5) (a) Evans, O. R.; Lin, W. Acc. Chem. Res. 2002, 35, 511. (b) Evans,
O. R.; Lin, W. Chem. Mater. 2001, 13, 2705.
(9) (a) Chae, H. K.; Siberio-Pe´rez, D. Y.; Kim, J.; Go, Y. B.; Eddaoudi,
M.; Matzger, A. J.; O’Keeffe, M.; Yaghi, O. M. Nature 2004, 427,
523. (b) Fe´rey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.;
Dutour, J.; Surble´, S.; Margiolaki, I. Science 2005, 309, 2040.
(10) (a) Uemura, K.; Matsuda, R.; Kitagawa, S. J. Solid State Chem. 2005,
178, 2420. (b) Bradshaw, D.; Claridge, J. B.; Cussen, E. J.; Prior, T.
J.; Rosseinsky, M. J. Acc. Chem. Res. 2005, 38, 273. (c) Kitagawa,
S.; Kazuhiro, U. Chem. Soc. ReV. 2005, 34, 109 and references cited
therein.
(11) (a) Cheetham, A. K.; Fe´rey, G.; Loiseau, T. Angew. Chem., Int. Ed.
1999, 38, 3268. (b) Davis, M. E. Nature 2002, 417, 813.
(12) (a) Fletcher, A. J.; Thomas, K. M. Langmuir 2000, 16, 6253. (b) Reid,
C. R.; Thomas, K. M. J. Phys. Chem. B 2001, 105, 10619.
(13) (a) Uemura, K.; Kitagawa, S.; Fukui, K.; Saito, K. J. Am. Chem. Soc.
2004, 126, 3817. (b) Wu, C. D.; Lin, W. Angew. Chem., Int. Ed. 2005,
44, 1958. (c) Kondo, A.; Noguchi, H.; Ohnishi, S.; Kajiro, H.; Tohdoh,
A.; Hattori, Y.; Xu, W.-C.; Tanaka, H.; Kanoh, H.; Kaneko, K. Nano
Lett. 2006, 6, 2581.
(6) (a) Matsuda, R.; Kitaura, R.; Kitagawa, S.; Kubota, Y.; Belosludov,
R. V.; Kobayashi, T. C.; Sakamoto, H.; Chiba, T.; Takata, M.;
Kawazoe, Y.; Mita, Y. Nature 2005, 436, 238. (b) Dincaˇ, M.; Long,
J. R. J. Am. Chem. Soc. 2005, 127, 9376. (c) Pan, L.; Adams, K. M.;
Hernandez, H. E.; Wang, X.; Zheng, C.; Hattori, Y.; Kaneko, K. J.
Am. Chem. Soc. 2003, 125, 3062. (d) Dybtsev, D. N.; Chun, H.; Yoon,
S. H.; Kim, D.; Kim, K. J. Am. Chem. Soc. 2004, 126, 32. (e) Pan,
L.; Parker, B.; Huang, X.; Olson, D. H.; Lee, J. Y.; Li, J. J. Am. Chem.
Soc. 2006, 128, 4180. (f) Llewellyn, P. L.; Bourrelly, S.; Serre, C.;
Filinchuk, Y.; Fe´rey, G. Angew. Chem., Int. Ed. 2006, 45, 7751. (g)
Humphrey, S. M.; Chang, J.-S.; Jhung, S. H.; Yoon, J. W.; Wood, P.
T. Angew. Chem., Int. Ed. 2006, 46, 272. (h) Ma, S.; Sun, D.; Wang,
X.-S.; Zhou, H.-C. Angew. Chem., Int. Ed. 2007, 47, 2458. (i) Rood,
J. A.; Noll, B. C.; Henderson, K. W. Inorg. Chem. 2006, 45, 5521.
(7) (a) Eddaoudi, K. J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keeffe, M.;
Yaghi, O. M. Science 2002, 295, 469. (b) Millward, A. R.; Yaghi, O.
M. J. Am. Chem. Soc. 2005, 127, 17998. (c) Latroche, M.; Surble, S.;
Serre, C.; Mellot-Draznieks, C.; Llewellyn, P. L.; Lee, J.-H.; Chang,
J.-S.; Jhung, S. H.; Fe´rey, G. Angew. Chem., Int. Ed. 2006, 45, 8227.
(14) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1461.
(15) Chen, B.; Ma, S.; Zapata, F.; Fronczek, F. R.; Lobkovsky, E. B.; Zhou,
H.-C. Inorg. Chem. 2007, 46, 1233.
3432 Inorganic Chemistry, Vol. 46, No. 9, 2007
10.1021/ic070338v CCC: $37.00
© 2007 American Chemical Society
Published on Web 04/04/2007

COMMUNICATION
Figure 1. µ3-Oxotrinickel basic carboxylate SBU (carbon, black; oxygen,
red; nickel, green).
Figure 2. (a) 2-fold interpenetrating network of PCN-5, viewed from the
[0 0 1] direction. (b) Space-filling model from the [1 0 0] direction showing
hydrophobic (white) and hydrophilic (red) channels.
lography, elemental analysis, and thermogravimetric analysis
(TGA).
Single-crystal X-ray crystallographic studies16 revealed that
PCN-5 crystallizes in monoclinic space group C2/m. PCN-5
adopts a trimeric µ3-oxo-centered basic carboxylate cluster
[Ni3O(O2CR)6(H2O)3]2- (Figure 1) as its secondary building
unit (SBU) with an average Ni-µ3-O distance of 2.019 Å.
In a SBU, the three Ni atoms and the µ3-O atom are on the
same plane. Each pair of Ni centers are bridged by two
carboxylate groups from two different TATB ligands, and
the coordination geometry of each Ni center is octahedral
when the terminal aqua ligand is considered (average Ni-O
distance 2.126 Å). These trigonal-planar basic carboxylate
clusters, [M3O(O2CR)6(L)3], where M represents trivalent
metal ions (Al3+, Cr3+, Fe3+),17 have been previously
employed as SBUs for the construction of MOFs. Trigonal-
planar basic carboxylate clusters with divalent metal ions,
however, are rare in both small molecules and MOFs.18
Each trinickel SBU connects six TATB ligands, and each
TATB ligand binds three trinickel SBUs to form a binodal
(3,6)-connected net. Similar to that found in other TATB
MOFs,19 π-π interaction between TATB ligand pairs has
also been observed in PCN-5. In previously reported TATB
MOFs, the triazine rings of each TATB pair are in the
staggered conformation, leading to strong π-π interaction.19
In PCN-5, however, the central triazine rings of each TATB
pair are in a dislocated conformation (Figure S1 in the
Supporting Information). The distance between the centers
of the two triazine rings is 4.471 Å, but the distance between
the two ligands is 3.385 Å, indicating π-π interactions.
Overall, PCN-5 possesses a 2-fold interpenetrated structure
(Figure 2a).
In the [1 0 0] direction, there exist two types of open
channels (Figure 2b): One is hydrophilic, with two trinickel
SBUs opposite to each other and a SBU-SBU distance of
4.928 Å (terminal O-terminal O). The other is hydrophobic,
surrounded by four TATB ligands, with a channel size of
5.334 × 4.977 Å (C-C). In the [0 1 0] direction, the trinickel
SBUs are connected by TATB ligands to form hydrophilic
channels with the distance between the terminal aqua ligands
of opposite SBUs 4.928 Å (O-O) (Figure S2 in the
Supporting Information), while in the [0 0 1] direction, large
channels containing opposite trinickel SBUs can be found
(Figure 2a). The shortest distance between two opposite
terminal aqua ligands is 11.413 Å (O-O).
TGA (Figure S4 in the Supporting Information) indicates
that the first weight loss of 23.1% from 50 to 200 °C
corresponds to the loss of five DMF guest molecules (calcd
24.0%), which is closely followed by the loss of two water
solvates and three aqua ligands (found 6.1%; calcd 6.0%)
on the SBU up to 300 °C. Decomposition of the TATB
ligands starts at 300 °C and ends at 560 °C with an overall
weight loss of 57.2% (calcd 57.5%), leaving a black residue
of NiO (found 13.6%; calcd 12.5) behind.
The permanent porosity of PCN-5 is verified by gas-
sorption isotherms (Figure 3) and powder X-ray diffraction
(PXRD) studies (Figure S3 in the Supporting Information).
(16) X-ray crystal data for PCN-5: C48H30N6O16Ni3, Mr ) 1122.91,
monoclinic, C2/m, a ) 30.175(3) Å, b ) 21.108(3) Å, c ) 16.762(2)
Å, R ) 90.00°, â ) 123.188(2)°, γ ) 90.00°, V ) 8934.7(18) Å3, Z
) 4, T ) 293 K, Fcalcd ) 0.835 g/cm3, R1 [I > 2σ(I)] ) 0.0476, wR2
) 0.1304, GOF ) 0.949.
(17) (a) Baethelet, K.; Riou, R.; Fe´rey, G. Chem. Commun. 2002, 2058.
(b) Serre, C.; Millange, F.; Surble´, S.; Fe´rey, G. Angew. Chem., Int.
Ed. 2004, 43, 2590. (c) Yang, G.; Raptis, R. G. Chem. Commun. 2004,
2058. (d) Fe´rey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.;
Dutour, J.; Surble´, S.; Margiolaki, I. Science 2005, 309, 2040. (e)
Sudik, A.; Coˆte´, A. P.; Yaghi, O. M. Inorg. Chem. 2005, 44, 2998.
(f) Sudik, A.; Coˆte´, A. P.; Wong-Foy, A.; O’Keeffe, M.; Yaghi, O.
M. Angew. Chem., Int. Ed. 2006, 45, 2528. (g) Loiseau, T.; Lecroq,
L.; Volkringer, C.; Marrot, J.; Fe´rey, G.; Haouas, M.; Taulelle, F.;
Bourrelly, S.; Llewellyn, P. L.; Latroche, M. J. Am. Chem. Soc. 2006,
128, 10223.
(18) (a) Reynolds, R. A., III; Yu, W. O.; Dunham, W. R.; Coucouvanis,
D. Inorg. Chem. 1996, 44, 2721. (b) Jia, J.; Lin, X.; Wilson, C.; Blake,
A. J.; Champness, N. R.; Hubberstey, P.; Walker, G.; Cussen, E. J.;
Schro¨der, Chem. Commun. 2007, 840.
(19) (a) Sun, D.; Ma, S.; Ke, Y.; Petersen, T. M.; Zhou, H. Chem. Commun.
2005, 2663. (b) Sun, D.; Ma, S.; Ke, Y.; Collins, D. J.; Zhou, H.-C.
J. Am. Chem. Soc. 2006, 128, 3896. (c) Ma, S.; Zhou, H.-C. J. Am.
Chem. Soc. 2006, 128, 11734. (d) Ma, S.; Sun, D.; Ambrogio, M.
W.; Fillinger, J. A.; Parkin, S.; Zhou, H.-C. J. Am. Chem. Soc. 2007,
129, 1858.
A freshly prepared sample of PCN-5 was soaked in
methanol for 3 days to remove DMF guest molecules.
Subsequently, the sample was soaked in dichloromethane
for 3 days more to remove methanol solvates and then
pumped under a dynamic vacuum at 25 °C overnight to
activate the sample.
Based on the TGA results and the activation temperature,
it can be inferred that the aqua ligands on the SBUs should
remain in the activated sample and the protonated water
solvates should stay connected to these terminal aqua ligands
through hydrogen bonding. Crystallographic studies showed
electron density for the water solvates, but a clear picture of
the hydrogen-bonding network could not be established
because the solvates are highly disordered. An attempt to
remove the aqua ligands and water solvates by heating other
samples at 100 °C or higher under a dynamic vacuum
resulted in the collapse of the framework.
Inorganic Chemistry, Vol. 46, No. 9, 2007 3433

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recently.25 The hysteretic hydrogen sorption thus may offer
the possibility of developing new porous MOFs, which can
upload hydrogen at high pressures and store it at low
pressures.25
To check the selective adsorption properties of PCN-5,
carbon dioxide and methane adsorption studies were carried
out at 195 K. As shown in Figure 3c, the carbon dioxide
uptake by PCN-5 at 195 K and 760 Torr can reach 210 mg/g
(4.8 mmol/g), while the methane uptake under the same
conditions is limited to 30 mg/g (1.9 mmol/g). The selective
adsorption of carbon dioxide (kinetic diameter 3.3 Å) over
methane (3.8 Å) can be attributed to the molecular-sieving
effect. When van der Waals radii of the channel wall are
considered, a channel with an atom-atom distance of 4.98
Å corresponds to an opening of about 3.3 Å. The 11.413 Å
channels shown in Figure 2a should be largely blocked by
the hydrogen-bonding network (vide supra). The boiling
point difference between the two gases may also contribute
to the adsorption selectivity. A similar molecular-sieving
effect has also been observed recently in manganese formate,6d
chromium terephthalate,6f a cobalt MOF,6g and a nickel
MOF.6h
In conclusion, an interpenetrating microporous nickel MOF
(PCN-5) constructed from a µ3-oxotrinickel basic carboxylate
SBU has been synthesized and structurally characterized.
Gas-sorption studies indicate that PCN-5 exhibits both
hysteretic hydrogen sorption and exciting gas-adsorption
selectivity. Future work will focus on developing MOFs with
high gas-adsorption selectivity and high hydrogen uptake.
Figure 3. (a) Nitrogen sorption isotherm at 77 K. (b) Hydrogen
adsorption-desorption isotherms at 77 K. (c) Carbon dioxide and methane
adsorption isotherms at 195 K.
The nitrogen sorption isotherm (Figure 3a) of an activated
sample reveals a Langmuir surface area of 225 m2/g and a
pore volume of 0.13 cm3/g. As shown in Figure 3a, the
nitrogen adsorption hysteresis can be attributed to the
dynamic feature of the framework that arises from the
hydrogen-bonding network formed by terminal aqua ligands
and water solvates in the large hydrophilic channel.1b,10a,20
This assessment is also consistent with the observed selective
adsorption behavior of PCN-5 (vide infra).
Acknowledgment. This work was supported by the
National Science Foundation (Grant CHE-0449634) and
Miami University. H.-C.Z. also acknowledges Research
Corp. for a Research Innovation Award and a Cottrell Scholar
Award.
Supporting Information Available: Structure figures, TGA
plots, PXRD data, and complete crystallographic data (CIF) for
PCN-5. This material is available free of charge via the Internet at
http://pubs.acs.org.
The hydrogen adsorption isotherm (Figure 3b) indicates
an uptake of 70 cm3/g (0.63 wt %) for PCN-5 at 77 K and
760 Torr. Because the hydrogen adsorption isotherm is not
saturated, a higher hydrogen uptake is expected under higher
pressures. The hydrogen adsorption data follow the Lang-
muir-Freundlich equation21 closely and predict a saturation
of 0.8 wt % for PCN-5 at 77 K. These values are lower than
those of other reported MOFs7c,19b-d,20,22 but comparable
with those of zeolites, ZSM-5 (0.7 wt %),6d and higher than
those of mesoporous silica materials (MCM-41, 0.5 wt %).23
As shown in Figure 3b, the sorption isotherm also displays
noticeable hysteresis because of the framework flexibility
arising from the hydrogen-bonding network. The kinetic
effect in narrow pores may also be a contributing factor to
the hysteresis because the adsorption/desorption kinetics were
very slow.24 Similar behavior has only been observed
IC070338V
(22) (a) Rowsell, J. L. C.; Millward, A. R.; Park, K. S.; Yaghi, O. M. J.
Am. Chem. Soc. 2004, 126, 5666. (b) Rowsell, J. L. C.; Eckart, J.
Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 14904. (c) Kesanli, B.;
Cui, Y.; Smith, M. R.; Bittner, E. W.; Bockrath, B. C.; Lin, W. Angew.
Chem., Int. Ed. 2005, 44, 72. (d) Sun, D.; Ke, Y.; Mattox, T. M.;
Betty, A. O.; Zhou, H.-C. Chem. Commun. 2005, 5447. (e) Chen, B.;
Ockwig, N. W.; Millward, A. R.; Contrereas, D. S.; Yaghi, O. M.
Angew. Chem., Int. Ed. 2005, 44, 4745. (f) Rowsell, J. L. C.; Yaghi,
O. M. J. Am. Chem. Soc. 2006, 128, 1304. (g) Wong-Foy, A. G.;
Matzger, A. J.; Yaghi, O. M. J. Am. Chem. Soc. 2006, 128, 3494. (h)
Pan, L.; Sander, M. B.; Huang, X.; Li, J.; Smith, M. R., Jr.; Bittner,
E. W.; Bockrath, B. C.; Johnson, J. K. J. Am. Chem. Soc. 2004, 126,
1308. (i) Lin, X.; Jia, J.; Zhao, X.; Thomas, K. M.; Blake, A. J.;
Walker, G. S.; Champness, N. R.; Hubberstey, P.; Schroder, M. Angew.
Chem., Int. Ed. 2006, 45, 7358. (j) Dincaˇ, M.; Dailly, A.; Liu, Y.;
Brown, C. M.; Neumann, D. A.; Long, J. R. J. Am. Chem. Soc. 2006,
128, 16876.
(23) (a) Gavrilov, V. Y. Kinet. Catal. 2005, 46, 642. (b) Jung, J. H.; Han,
W. S.; Rim, J. A.; Lee, S. J.; Cho, S. J.; Kim, S. Y.; Kang, J. K.;
Shinkai, S. Chem. Lett. 2006, 35, 32.
(20) Chen, B.; Ma, S.; Zapata, F.; Lobkovsky, E. B.; Yang, J. Inorg. Chem.
(24) Navarro, J. A. R.; Barea, E.; Salas, J. M.; Masciocchi, N.; Galli, S.;
Sironi, A.; Ania, C. O.; Parra, J. B. Inorg. Chem. 2006, 45, 2397.
(25) Zhao, X.; Xiao, B.; Fletcher, A. J.; Thomas, K. M.; Bradshaw, D.;
Rosseinsky, M. J. Science 2004, 306, 1012.
2006, 45, 5718.
(21) Yang, R. T. Gas Adsorption by Adsorption Processes; Butterworth:
Boston, 1997.
3434 Inorganic Chemistry, Vol. 46, No. 9, 2007