C O M M U N I C A T I O N S
Supporting Information Available: Detailed experimental proce-
dures, including synthesis of L0 and L1, crystallographic data (in CIF
format), PXRD, TGA of IRMOF-76 and -77, and detailed sorption
studies of IRMOF-77 and quinoline-exchanged IRMOF-77. This
References
(1) (a) Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi,
M.; Kim, J. Nature 2003, 423, 705–714. (b) Kitagawa, S.; Kitaura, R.;
Noro, S. Angew. Chem., Int. Ed. 2004, 43, 2334–2375. (c) Fe´rey, G. Chem.
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Yaghi, O. M. Handbook of Heterogeneous Catalysis, 2nd ed.; Wiley-VCH
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(2) Wang, Z.; Cohen, S. M. Chem. Soc. ReV. 2009, 38, 1315–1329.
(3) Postsynthetic modifications producing immobilized transition metal coor-
dination complexes: (a) Wu, C.-D.; Hu, A.; Zhang, L.; Lin, W. J. Am.
Chem. Soc. 2005, 127, 8940–8941. (b) Ingelson, M. J.; Barrio, J. P.;
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Figure 2. N2 isotherm for IRMOF-77 measured at 77 K.
(4) Yamada, T.; Kitagawa, H. J. Am. Chem. Soc. 2009, 131, 6312–6313.
(5) (a) Nolan, S. P. N-Heterocyclic Carbenes in Synthesis; Wiley-VCH:
Weubgeunm, Germany, 2006. (b) Hahn, F. E.; Jahnke, M. C. Angew. Chem.,
Int. Ed. 2008, 47, 3122–3172. (c) Marion, N.; Nolan, S. P. Acc. Chem.
Res. 2008, 41, 1440–1449.
(6) Cu(I)-NHC bond formation during MOF synthesis with use of a bent
link: (a) Chun, J.; Jung, I. G.; Kim, H. J.; Park, M.; Lah, M. S.; Son, S. U.
Inorg. Chem. 2009, 48, 6353–6355. (b) Chun, J.; Lee, H. S.; Jung, I. G.;
Lee, S. W.; Kim, H. J.; Son, S. U. Organometallics 2010, 29, 1518–1521.
(7) Imidazolium precursors integrated within MOF: (a) Fei, Z.; Geldbach, T. J.;
Zhao, D.; Scopelliti, R.; Dyson, P. J. Inorg. Chem. 2005, 44, 5200–5202.
(b) Fei, Z.; Geldbach, T. J.; Scopelliti, R.; Dyson, P. J. Inorg. Chem. 2006,
45, 6331–6337. (c) Han, L.; Zhang, S.; Wang, Y.; Yan, X.; Lu, X. Inorg.
Chem. 2009, 48, 786–788. (d) Lee, J. Y.; Roberts, J. M.; Farha, O. K.;
Sarjeant, A. A.; Scheidt, K. A.; Hupp, J. T. Inorg. Chem. 2009, 48, 9971–
9973. (e) Crees, R. S.; Cole, M. L.; Hanton, L. R.; Sumby, C. J. Inorg.
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Figure 3. PXRD patterns of as-synthesized IRMOF-77 (red) and quinoline-
exchanged IRMOF-77 (blue) and simulated PXRD pattern from single-
crystal X-ray structure (black).
(9) Neto, B. A. D.; Lopes, A. S.; Wust, M.; Costa, V. E. U.; Ebeling, G.;
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(10) See Supporting Information for details.
(11) Crystal data after SQUEEZE (Cu ΚR radiation, λ ) 1.54178 Å): IRMOF-
j
76, Zn4O(C23H15N2O4)3, Mr ) 1427.59, cubic Fm3m, a ) 42.9245(2) Å, V
) 79088.9(6) Å3, Z ) 8, Dc ) 0.240 g cm-3, 1260 independent reflections
observed, R1 ) 0.0549 (I > 2σ(I)), wR2 ) 0.2166 (all data), and GOF )
To examine the reactivity of the immobilized Pd(II) centers of
IRMOF-77, ligand exchange experiments were carried out by
immersing as-synthesized crystals of IRMOF-77 in 4% v/v quino-
line/DMF solution for 1 day at room temperature. A comparison
between the powder X-ray diffraction (PXRD) patterns before and
after exchange reveals that the framework remains intact during
the exchange process (Figure 3), which is also supported by porosity
measurements.10 No signal from the pyridine protons is observed
in the 1H NMR spectrum of the digested MOF after ligand
exchange. Only the signals from quinoline are observed, with the
expected molar stoichiometry (carboxylate link:quinoline ) 1:1).10
Retention of the NHC-Pd bond is confirmed by the 13C CP/MAS
solid-state NMR spectrum (before, 154.1 ppm; after, 152.9 ppm).
These results indicate the presence of an NHC-PdI2(quinoline)
complex after ligand exchange.18
j
0.912; IRMOF-77, Zn4O(C28H21I2N3O4Pd)3, Mr ) 2748.51, trigonal R3c,
a ) b ) 31.0845(4) Å, c ) 71.018(2) Å, V ) 59427(2) Å3, Z ) 12, Dc )
0.922 g cm-3, 3946 independent reflections observed, R1 ) 0.0560 (I >
2σ(I)), wR2 ) 0.1389 (all data), and GOF ) 0.950.
(12) (a) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keeffe,
M.; Yaghi, O. M. Science 2002, 295, 469–472. (b) Bae, Y.-S.; Dubbeldam,
D.; Nelson, A.; Walton, K. S.; Hupp, J. T.; Snurr, R. Q. Chem. Mater.
2009, 21, 4768–4777.
(13) O’Keeffe, M.; Peskov, M. A.; Ramsden, S. J.; Yaghi, O. M. Acc. Chem.
Res. 2008, 41, 1782–1789.
(14) Examples of using metalloligands to produce heterometallic MOFs: (a)
Kitaura, R.; Onoyama, G.; Sakamoto, H.; Matsuda, R.; Noro, S.; Kitagawa,
S. Angew. Chem., Int. Ed. 2004, 43, 2684–2687. (b) Halpar, S. R.; Do, L.;
Stork, J. R.; Cohen, S. M. J. Am. Chem. Soc. 2006, 128, 15255–15268. (c)
Cho, S.-H.; Ma, B.; Nguyen, S. T.; Hupp, J. T.; Albrecht-Schmitt, T. E.
Chem. Commun. 2006, 2563–2565. (d) Szeto, K. C.; Lillerud, K. P.; Tilset,
M.; Bjorgen, M.; Prestipino, C.; Zecchina, A.; Lamberti, C.; Bordiga, S. J.
Phys. Chem. B 2006, 110, 21509–21520. (e) Szeto, K. C.; Kongshaug,
K. O.; Jakobsen, S.; Tilset, M.; Lillerud, K. P. Dalton Trans. 2008, 2054–
2060.
(15) Tranchmontagne, D. J.; Mendoza-Corte´s, J. L.; O’Keeffe, M.; Yaghi, O. M.
Chem. Soc. ReV. 2009, 38, 1257–1283.
In conclusion, the structures of IRMOF-76 and -77 demonstrate
the successful application of our strategy to immobilize Pd(II)-NHC
organometallic complexes in MOFs without losing the MOF’s
porosity and its structural order.
(16) Elemental analysis for IRMOF-77 [Zn4O(C28H21I2N3O4Pd)3 ·4H2O] calcd:
C, 35.77; H, 2.54; I, 26.99; N, 4.47; Pd, 11.32; Zn, 9.28. Found: C, 35.04;
H, 2.62; I, 26.92; N, 4.71; Pd, 9.67; Zn, 9.32%.
(17) Selected example: Han, Y.; Huyuh, H. V.; Tan, G. K. Organometallics
2007, 26, 6447–6452.
(18) (a) Chemical shifts of C2 of N,N′-dimethylbenzoimidazolium salt and a
metal-free NHC generated from the salt are reported as 143 and 225 ppm,
respectively: Tapu, D.; Dixon, D. A.; Roe, C. Chem. ReV. 2009, 109, 3385–
3407. (b) No significant change of 13C chemical shift after ligand exchange
suggested the coligand (L) of NHC-PdX2(L) has donor strength similar
to that of pyridine: Huynh, H. V.; Han, Y.; Jothibasu, R.; Yang, J. A.
Organometallics 2009, 28, 5394–5404.
Acknowledgment. We thank BASF SE (Ludwigshafen,
Germany), the U.S. DOE (DE-FG02-08ER15935), and the U.S.
Army (W911NF-06-1-0405) for funding and H. Deng and D. Britt
(Yaghi group) for experimental assistance and invaluable discussion.
K.O. thanks the Japan Society for the Promotion of Sciences for
financial support.
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