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ceased after the catalyst was filtered off, suggesting no
leaching of homogeneous active species (Fig. S18). The catalyst
can be readily isolated by filtration, and after adequate
washing and re-activation, the used catalyst remains highly
active (99% conversion, 1 h). XRD measurements indicate that
the framework retains its integrity after use (Fig. S15). The
catalytic activity of UiO-66-CH NMe -14 was compared with
O’Keeffe and O. M. Yaghi, Science, 2002, 295, 469; (b) J.
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Gascon, U. Aktay, M. D. Hernandez-Alonso, G. P. M. van Klink
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H. Deng, C. J. Doonan, H. Furukawa, R. B. Ferreira, J. Towne,
C. B. Knobler, B. Wang and O. M. Yaghi, Science, 2010, 327
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46-850; (e) P. Li, Q. Sui, M.-Y. Guo, S.-L. Yang, R. Bu and E.-
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2
Q. Gao, Chem. Commun., 2020, 56, 5929-5932; (f) L.-J. Zhou,
W. Sun, N.-N. Yang, P. Li, T. Gong, W.-J. Sun, Q. Sui and E.-Q.
Gao, ChemSusChem, 2019, 12, 2202-2210.
those of previous MOF catalysts reported for the same
reaction (Table S3). As can be seen, a general trend is that the
MOFs with the aliphatic amino groups are more active than
those with aromatic ones. The TOFs of UiO-66-CH NMe -14
6
(a) H. Fei and S. M. Cohen, Chem. Commun., 2014, 50, 4810-
4
812; (b) M. Banerjee, S. Das, M. Yoon, H. J. Choi, M. H.
2
2
-1
Hyun, S. M. Park, G. Seo and K. Kim, J. Am. Chem. Soc., 2009,
(
260-533 h ) are generally higher than those of the catalysts at
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31, 7524-7525; (c) S. M. Cohen, Chem. Rev., 2012, 112, 970-
000; (d) X.-M. Yin, L.-L. Gao, P. Li, R. Bu, W.-J. Sun and E.-Q.
comparable conversion levels, and in particular the
comparison between UiO-66-derived MOFs reveals that our
Gao, ACS Appl. Mater. Interfaces, 2019, 11, 47112-47120; (e)
H. Fei, J. Shin, Y. S. Meng, M. Adelhardt, J. Sutter, K. Meyer
and S. M. Cohen, J. Am. Chem. Soc., 2014, 136, 4965-4973.
(a) X.-H. Li, Y.-W. Liu, Y. Lu, Z. Zhang, H.-R. Tian, S.-M. Liu and
S.-X. Liu, Chem. Commun., 2020, 56, 1641-1644; (b) B. Ren, Y.
Li, D. Meng, J. Li, S. Gao and R. Cao, J. Colloid Interface Sci.,
MOF is more efficient than that UiO-66-NH-RNH , which
possesses both aromatic and aliphatic amino groups.
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To conclude, we have shown for the first time that the
metal-catalyzed Leuckart reactions of formyl groups with N,N-
dialkylformamide occur concomitantly with solvothermal
assembly of MOFs of different topologies, which provides a
one-pot route to synthesize the MOFs functionalized with
aliphatic tertiary amino groups. UiO-66-CH NMe was shown
2
020, 579, 842-852; (c) U. Ryu, J. Yoo, W. Kwon and K. M.
Choi, Inorg. Chem., 2017, 56, 12859-12865.
(a) J.-P. Zhang, Y.-Y. Lin, X.-C. Huang and X.-M. Chen, J. Am.
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Cheng, Q. Yue, W.-W. Sun and E.-Q. Gao, Chem. Commun.,
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to be efficient heterogeneous base catalysts for Knoevenagel
condensation. Excellent activity has been achieved for the
mixed-linker MOFs showing the balance between the base
group content and the porosity. The results illustrate the
intriguing strategy of MOF functionalization through in situ
group transformation, in parallel with pre- and postsynthetic
transformation. The challenge and opportunity are to find
appropriate organic reactions compatible with the synthetic
conditions of desired MOFs.
2
008, 847-849; (c) H. Zhao, Z.-R. Qu, H.-Y. Ye and R.-G. Xiong,
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The work was funded by the NSFC (No. 21773070,
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1701137 and 21971069) and STIP (No. 2019L0837).
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1 C. Kutzscher, G. Nickerl, I. Senkovska, V. Bon and S. Kaskel,
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Conflicts of interest
There are no conflicts to declare.
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