Published on Web 09/17/2010

Metal Insertion in a Microporous Metal-Organic Framework Lined with

2,2′-Bipyridine
Eric D. Bloch,† David Britt,‡ Chain Lee,‡ Christian J. Doonan,‡,§ Fernando J. Uribe-Romo,‡
Hiroyasu Furukawa,‡ Jeffrey R. Long,*,† and Omar M. Yaghi*,‡
Department of Chemistry, UniVersity of California, Berkeley, California, 94720, Center for Reticular Chemistry at
the California NanoSystems Institute, Department of Chemistry and Biochemistry, UniVersity of California-Los
Angeles, 607 East Charles E. Young DriVe, Los Angeles, California 90095, and School of Chemistry & Physics, The
UniVersity of Adelaide, Adelaide, South Australia 5005, Australia
Received August 3, 2010; E-mail: [email protected]; [email protected]

Abstract: Reaction of AlCl3 · 6H2O with 2,2′-bipyridine-5,5′-dicar-

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boxylic acid (H2bpydc) affords Al(OH)(bpydc) (1, MOF-253), the

first metal-organic framework with open 2,2′-bipyridine (bpy)
coordination sites. The material displays a BET surface area of
2160 m2/g and readily complexes metals to afford, for example,
1 · xPdCl2 (x ) 0.08, 0.83) and 1 · 0.97Cu(BF4)2. EXAFS spec-
troscopy performed on 1 · 0.83PdCl2 reveals the expected square
planar coordination geometry, matching the structure of the model
complex (bpy)PdCl2. Significantly, the selectivity factor for binding
CO2 over N2 under typical flue gas conditions is observed to
increase from 2.8 in 1 to 12 in 1 · 0.97Cu(BF4)2.

Owing to their high surface areas and tunable pore functionality,

Figure 1. Synthesis and representative structure of Al(OH)(bpydc) (1,
metal-organic frameworks are currently under investigation for a MOF-253), with subsequent insertion of PdCl2 into open bpy ligand sites.
variety of potential applications, including gas storage,1 gas Orange octahedra represent Al atoms, while yellow, green, red, blue, and
separations,2 and catalysis.3 Of particular promise are frameworks gray spheres represent Pd, Cl, O, N, and C atoms, respectively; H atoms
with surfaces bearing exposed metal centers, since these can are omitted for clarity.
dramatically enhance (selective) gas uptake or serve as a source of
200 °C, consistent with loss of 2.6 solvent molecules per formula unit,
catalytic activity.4 Such metal sites have typically been created
with no further weight loss up to 400 °C. Accordingly, the solid was
either by desolvation of a framework featuring metal-bound solvent
soaked in methanol and then heated at 250 °C under dynamic vacuum
molecules or via some form of postsynthetic modification to the
for 24 h to yield the fully desolvated framework Al(OH)(bpydc) (1).
organic bridging ligands.5 The direct formation of frameworks
X-ray powder diffraction data show 1 to be isostructural with
bearing chelating ligand sites that are open to metal insertion is
Al(OH)(bpdc).7 A full-pattern decomposition of the data was
rare,3a,b,6 since typically metal binding at these sites would occur
performed through a Pawley refinement using the Al(OH)(bpdc)
during framework synthesis. In our efforts to generate compounds
unit cell parameters as a starting point, resulting in refined
of this type, we considered the possibility that a hard oxophilic
orthorhombic unit cell parameters of a ) 23.59(10) Å, b ) 6.91(3)
metal cation might preferentially coordinate the carboxylate groups
Å, and c ) 19.84(8) Å. Based upon the refinement, it is clear that
of a mixed donor ligand such as 2,2′-bipyridine-5,5′-dicarboxylate
Al(OH)(bpydc) crystallizes as an sra net with a rod-shaped
(bpydc2-), leading to a framework with the softer donor groups
secondary building unit in an extended MIL-53 structure. A crystal
available to bind metals. Here, we show that this strategy can indeed
model of the structure was built by replacing the biphenyl moiety
be successfully employed in generating Al(OH)(bpydc) (MOF-253),
of Al(OH)(bpdc) with bipyridine (see Figure 1). Here, one-
the first metal-organic framework featuring open 2,2′-bipyridine
dimensional chains of hydroxide-bridged, octahedrally coordinated
(bpy) ligand sites. Subsequent complexation of Pd2+ and Cu2+ is
Al3+ cations are linked via bpydc2- ligands to give a three-
demonstrated, with the latter resulting in a material that exhibits a
dimensional framework with rhombic channels running along the
significantly enhanced selectivity for the adsorption of CO2 over
b axis. Note that the pyridine rings should have only a small energy
N2.
barrier associated with rotation away from the coplanar configu-
The synthesis of Al(OH)(bpydc) was accomplished in direct analogy ration depicted, thereby enabling insertion of up to one metal center
with the recently reported framework Al(OH)(bpdc) (bpdc2- ) 4,4′- per bpy unit.
biphenyldicarboxylate).7 Reaction of H2bpydc with AlCl3 · 6H2O in NMR spectroscopy was employed to confirm the bulk composi-
DMF at 120 °C for 24 h afforded Al(OH)(bpydc) · 2.6DMF tion of 1 (see Supporting Information, Figures S5-S7). As in the
(1 · 2.6DMF) as a white microcrystalline solid. Thermogravimetric activated form of MIL-53,8 the 1H MAS NMR spectrum exhibits
analysis of the product revealed a weight loss of 40% upon heating to two broad peaks, attributable to the aromatic and bridging hydroxide
protons. The six sharp resonances in the 13C cross-polarization MAS
†
University of California-Berkeley. NMR spectrum confirm the presence of bpydc2- in the structure.
‡
University of California-Los Angeles.
§
The University of Adelaide. Most importantly, the 27Al MAS NMR spectrum shows a solitary
14382 9 J. AM. CHEM. SOC. 2010, 132, 14382–14384 10.1021/ja106935d  2010 American Chemical Society
 COMMUNICATIONS

Figure 2. Isotherms for the adsorption of N2 at 77 K in 1 (red), 1 · 0.08PdCl2 Figure 4. Adsorption isotherms collected at 298 K for the uptake of CO2
(green), 1 · 0.97Cu(BF4)2 (blue), and 1 · 0.83PdCl2 (orange). Filled and open in 1 (green triangles) and 1 · 0.97Cu(BF4)2 (green squares) and for the uptake
circles represent adsorption and desorption data, respectively. of N2 in 1 (blue triangles) and 1 · 0.97Cu(BF4)2 (blue squares). Filled and
open symbols represent adsorption and desorption, respectively.

geometry, with two Cl- ions and two N atoms from bpy binding
the Pd2+ center at distances of 2.296(1) and 2.038(3) Å, respectively
(see Figure 1). Note that these bond distances are in good agreement
with crystallographic data obtained for the analogous molecular
complex (bpy)PdCl2.9
Insertion of metal salts within 1 can be expected to create electric
dipoles on the surface that render the material suitable for gas
separations.2 Indeed, as shown in Figure 4, 1 · 0.97Cu(BF4)2 was
found to display a significantly enhanced selectivity for the
adsorption of CO2 over N2 under conditions relevant to its capture
from flue gas. Specifically, at 298 K, the selectivity factor, calculated
Figure 3. Pd K-edge EXAFS Fourier transforms and EXAFS spectrum as the mass of CO2 taken up at 0.15 bar divided by the mass of N2
(inset) for 1 · 0.83PdCl2. Solid lines show the experimental data, and dashed taken up at 0.75 bar, is seen to increase from 2.8 in 1 to 12 in
red lines show the best fits. 1 · 0.97Cu(BF4)2. Consistently, the average isosteric heat of CO2
adsorption, as calculated using isotherm data collected at 298, 303,
signal at δ ) -7.38 ppm, consistent with the presence of a single and 308 K, was found to increase from 23 to 30 kJ/mol upon
six-coordinate Al3+ site. The observation of just one 27Al resonance insertion of Cu(BF4)2 into the bpy sites of 1 (see Supporting
indicates that the bpy ligands are not coordinated by aluminum Information, Figures S10 and S11). Thus, metal-loaded variants of
and should therefore be available for the postsynthetic chelation 1 are well worthy of further study as CO2 capture materials.
of various other metal centers. The foregoing results demonstrate the ability of mixed donor
Low-pressure N2 adsorption measurements performed on 1 at ligands to select for hard metal cations during framework assembly,
77 K revealed a type I adsorption isotherm characteristic of a resulting in the first bpy-lined microporous material. Given the
microporous solid (see Figure 2, red circles). Fits to the data gave ubiquitous role of the bpy ligand in coordination chemistry, we
a pore volume of 0.89 cm3/g, together with BET and Langmuir anticipate that this framework will provide a platform for the
surface areas of 2160 and 2490 m2/g, respectively. The latter value insertion of a wide variety of metal centers, leading to a broad range
is in good agreement with the Langmuir surface area of 2335 m2/g of properties and applications.
reported for Al(OH)(bpdc).7
The accessibility of the chelating bpy units within the framework Acknowledgment. This research was funded through the Center
of 1 was confirmed by soaking the solid in acetonitrile solutions for Gas Separations Relevant to Clean Energy Technologies, an
of PdCl2 and Cu(BF4)2 to afford 1 · xPdCl2 (x ) 0.08, 0.83) and Energy Frontier Research Center funded by the U.S. Department
1 · 0.97Cu(BF4)2, as confirmed by elemental analyses. Thermogravi- of Energy, Office of Science, Office of Basic Energy Sciences,
metric analysis showed these metal-loaded samples to exhibit weight under Award No. DE-SC0001015. EXAFS measurements were
losses at 125 °C of 28%, 15%, and 25%, respectively, with no collected at the Stanford Synchrotron Radiation Lightsource (SSRL),
additional loss occurring up to 350 °C (see Supporting Information, a national user facility operated by Stanford University on behalf
Figure S8). As evidenced by powder X-ray diffraction, NMR of the Department of Energy.
spectroscopy, and infrared spectroscopy, the underlying framework Supporting Information Available: Detailed synthetic procedures
structure is maintained upon metal complexation. Consistent with and additional characterization data. This material is available free of
the formulations of 1 · 0.08PdCl2, 1 · 0.83PdCl2, and 1 · 0.97Cu(BF4)2, charge via the Internet at http://pubs.acs.org.
N2 adsorption measurements at 77 K resulted in type I adsorption
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