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product formation (11% yield after 24 h, see Fig. S5, ESI†), which is
comparable to the control experiment (14% yield). In addition, when
UiO-67 was used in conjunction with the pure strut UiO-67-Urea
framework as catalysts (1 : 1 molar ratio), no significant synergistic
improvement in catalysis was observed (17% yield, see Fig. S5, ESI†).
From these UiO-67-based experiments, it is evident that the
solvothermal synthesis of UiO-67-Urea/bpdc indeed results in indi-
vidual crystals including both bpdc and urea struts as opposed to a
physical mixture of UiO-67 and UiO-67-Urea crystals. Furthermore,
the urea sites in the UiO-67-Urea/bpdc framework likely play an
essential role as HBD catalysts in the Henry reactions.
C. A. Bauer, R. K. Bhakta and R. J. T. Houk, Chem. Soc. Rev., 2009,
38, 1330.
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7
(a) H.-J. Son, S. Jin, S. Patwardhan, S. J. Wezenberg, N. C. Jeong,
M. So, C. E. Wilmer, A. A. Sarjeant, G. C. Schatz, R. Q. Snurr,
O. K. Farha, G. P. Wiederrecht and J. T. Hupp, J. Am. Chem. Soc.,
2013, 135, 862; (b) S. Jin, H.-J. Son, O. K. Farha, G. P. Wiederrecht
and J. T. Hupp, J. Am. Chem. Soc., 2013, 135, 955; (c) C. Y. Lee,
O. K. Farha, B. J. Hong, A. A. Sarjeant, S. T. Nguyen and J. T. Hupp,
J. Am. Chem. Soc., 2011, 133, 15858; (d) C. A. Kent, B. P. Mehl, L. Ma,
J. M. Papanikolas, T. J. Meyer and W. Lin, J. Am. Chem. Soc., 2010,
1
32, 12767.
(a) J. Della Rocca, D. Liu and W. Lin, Acc. Chem. Res., 2011, 44, 957;
(b) P. Horcajada, C. Serre, M. Vallet-Regi, M. Sebban, F. Taulelle and
G. F ´e rey, Angew. Chem., Int. Ed., 2006, 45, 5974.
8
9
J. An and N. L. Rosi, J. Am. Chem. Soc., 2010, 132, 5578.
The efficacy of the mixed UiO-67-Urea/bpdc framework as a
Henry reaction catalyst was further examined using a more challen-
ging arylaldehyde, the electron-donating p-methoxybenzaldehyde.
To our delight, UiO-67-Urea/bpdc promotes the reaction between
(a) O. K. Farha, A. M. Shultz, A. A. Sarjeant, S. T. Nguyen and
J. T. Hupp, J. Am. Chem. Soc., 2011, 133, 5652; (b) J. Lee, O. K. Farha,
J. Roberts, K. A. Scheidt, S. T. Nguyen and J. T. Hupp, Chem. Soc.
Rev., 2009, 38, 1450; (c) L. Ma, C. Abney and W. Lin, Chem. Soc. Rev.,
2009, 38, 1248.
p-methoxybenzaldehyde and nitromethane to form 1-(4-methoxy- 10 (a) S. Biswas and P. Van der Voort, Eur. J. Inorg. Chem., 2013, 2154;
(
b) J. B. DeCoste, G. W. Peterson, H. Jasuja, T. G. Glover, Y.-g. Huang and
phenyl)-2-nitroethanol much more efficiently than UiO-67-Urea.
While the yield achieved with UiO-67-Urea/bpdc is modest (48%),
it is five-fold greater than obtained with UiO-67-Urea (10%) and
ca. ten-fold greater (or more) than obtained in a control experiment
K. S. Walton, J. Mater. Chem. A, 2013, 1, 5642; (c) H. Wu, T. Yildirim and
W. Zhou, J. Phys. Chem. Lett., 2013, 4, 925; (d) V. Guillerm, F. Ragon,
M. Dan-Hardi, T. Devic, M. Vishnuvarthan, B. Campo, A. Vimont,
G. Clet, Q. Yang, G. Maurin, G. F ´e rey, A. Vittadini, S. Gross and
C. Serre, Angew. Chem., Int. Ed., 2012, 51, 9267; (e) Y. Huang, W. Qin,
Z. Li and Y. Li, Dalton Trans., 2012, 41, 9283; ( f ) A. Schaate, P. Roy,
A. Godt, J. Lippke, F. Waltz, M. Wiebcke and P. Behrens, Chem.–Eur. J.,
(
o5%). Overall, the catalysis results illustrate the catalytic enhance-
ment obtainable by utilizing a heteroleptic framework, UiO-67-Urea/
bpdc, over the homoleptic framework, UiO-67-Urea.
2
011, 17, 6643; (g) M. Kandiah, M. H. Nilsen, S. Usseglio, S. Jakobsen,
U. Olsbye, M. Tilset, C. Larabi, E. A. Quadrelli, F. Bonino and
A functional, sterically demanding urea strut was successfully
K. P. Lillerud, Chem. Mater., 2010, 22, 6632.
incorporated into a UiO-67-based framework through a mixed-strut 11 M. J. Katz, Z. J. Brown, Y. J. Col o´ n, P. W. Siu, K. A. Scheidt,
R. Q. Snurr, J. T. Hupp and O. K. Farha, Chem. Commun., 2013,
de novo strategy with bpdc. PXRD analysis confirmed that the
49, 9449.
resulting UiO-67-Urea/bpdc is isostructural to the non-functionalized
UiO-67. In addition, UiO-67-Urea/bpdc framework features large
pores, i.e. similar to those of a linker-deficient version UiO-67 frame-
work, significantly greater than expected for defect-free UiO-67. The
mixed strut UiO-67-Urea/bpdc framework is active as a HBD catalyst
in promoting Henry reactions and engenders greater product for-
mation than does its pure-strut analogue, UiO-67-Urea, which exhibits
much smaller pore sizes. The ability to incorporate other functional,
organocatalytic struts of sophisticated design through this mixed strut
strategy will no doubt broaden the utility of UiO-67 and its derivatives
in catalysis and other applications.
1
2 For examples of UiO-67-based catalysis, see: (a) C. Wang, Z. Xie,
K. E. deKrafft and W. Lin, J. Am. Chem. Soc., 2011, 133, 13445;
(
b) M. Saito, T. Toyao, K. Ueda, T. Kamegawa, Y. Horiuchi and
M. Matsuoka, Dalton Trans., 2013, 42, 9444.
1
3 For examples of UiO-66-based catalysis, see: (a) F. Vermoortele,
B. Bueken, G. Le Bars, B. Van de Voorde, M. Vandichel,
K. Houthoofd, A. Vimont, M. Daturi, M. Waroquier, V. Van Speybroeck,
C. Kirschhock and D. E. De Vos, J. Am. Chem. Soc., 2013, 135, 11465;
(b) M. Pintado-Sierra, A. M. Rasero-Almansa, A. Corma, M. Iglesias and
F. Sanchez, J. Catal., 2013, 299, 137; (c) J. Kim, S.-N. Kim, H.-G. Jang,
G. Seo and W.-S. Ahn, Appl. Catal., A, 2013, 453, 175.
1
4 (a) J. M. Roberts, B. M. Fini, A. A. Sarjeant, O. K. Farha, J. T. Hupp
and K. A. Scheidt, J. Am. Chem. Soc., 2012, 134, 3334; (b) X.-W. Dong,
T. Liu, Y.-Z. Hu, X.-Y. Liu and C.-M. Che, Chem. Commun., 2013,
49, 7681.
OKF and JTH gratefully acknowledge financial support from
DTRA (grant no. HDTRA1-10-1-0023)
1
5 For selected reviews on homogeneous HBD catalysis, see: (a) Z. Zhang
and P. R. Schreiner, Chem. Soc. Rev., 2009, 38, 1187; (b) S. J. Connon,
Chem. Commun., 2008, 2499; (c) A. G. Doyle and E. N. Jacobsen, Chem.
Rev., 2007, 107, 5713; (d) C. Palomo, M. Oiarbide and A. Laso, Eur. J.
Org. Chem., 2007, 2561; (e) J. Seayad and B. List, Org. Biomol. Chem.,
2005, 3, 719; ( f ) F. A. Luzzio, Tetrahedron, 2001, 57, 915.
Notes and references
1
2
3
(a) M. O’Keeffe, M. A. Peskov, S. J. Ramsden and O. M. Yaghi, Acc.
Chem. Res., 2008, 41, 1782; (b) G. F ´e rey, Chem. Soc. Rev., 2008, 37, 191; 16 There are currently no specific examples of Henry reactions catalyzed by
(c) S. Horike, S. Shimomura and S. Kitagawa, Nat. Chem., 2009, 1, 695.
HBD MOFs. For general examples, see: (a) L.-X. Shi and C.-D. Wu, Chem.
Commun., 2011, 47, 2928; (b) J.-M. Gu, W.-S. Kim and S. Huh, Dalton
Trans., 2011, 40, 10826; (c) H. Yu, J. Xie, Y. Zhong, F. Zhang and W. Zhu,
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L. Zhang and C.-Y. Su, Chem.–Asian. J., 2012, 7, 2796; (e) T. Arai,
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O. K. Farha, I. Eryazici, N. C. Jeong, B. G. Hauser, C. E. Wilmer,
A. A. Sarjeant, R. Q. Snurr, S. T. Nguyen, A. O. Yazaydin and
J. T. Hupp, J. Am. Chem. Soc., 2012, 134, 15016.
(a) O. K. Farha, A. O. Yazaydin, I. Eryazici, C. D. Malliakas,
B. G. Hauser, M. G. Kanatzidis, S. T. Nguyen, R. Q. Snurr and
J. T. Hupp, Nat. Chem., 2010, 2, 944; (b) J. Sculley, D. Yuan and
H.-C. Zhou, Energy Environ. Sci., 2011, 4, 2721; (c) L. J. Murray, 17 V. K. Ol’khovik, A. A. Pap, V. A. Vasilevskii, N. A. Galinovskii and
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(a) J.-R. Li, R. J. Kuppler and H.-C. Zhou, Chem. Soc. Rev., 2009, 18 A similar strategy has recently been employed to access catalytically
8, 1477; (b) D. Britt, H. Furukawa, B. Wang, T. G. Glover and active Ir, Re and Ru doped UiO-67 frameworks, see ref. 12a.
O. M. Yaghi, Proc. Natl. Acad. Sci. U. S. A., 2009, 106, 20637; (c) J. An, 19 Samples of THF exchanged UiO-67-Urea/bpdc and UiO-67-Urea were
S. J. Geib and N. L. Rosi, J. Am. Chem. Soc., 2010, 132, 38; activated via supercritical CO . The PXRD pattern of UiO-67-Urea/
d) Y.-S. Bae, A. M. Spokoyny, O. K. Farha, R. Q. Snurr, J. T. Hupp
4
5
3
2
(
bpdc did not change after activation (see Fig. S3, ESI†). For compar-
ison, the BET surface area of the parent UiO-67 synthesized by this
and C. A. Mirkin, Chem. Commun., 2010, 46, 3478.
2
ꢀ1
(a) L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. Van Duyne
route was 2500 m g (see ref. 11).
and J. T. Hupp, Chem. Rev., 2012, 112, 1105; (b) M. D. Allendorf, 20 For TGA of UiO-67-Urea/bpdc and UiO-67-Urea, see Fig. S4, ESI†.
1
0922 Chem. Commun., 2013, 49, 10920--10922
This journal is c The Royal Society of Chemistry 2013