Journal of the American Chemical Society
Page 4 of 5
J. K.; Fujita, M. Angew. Chem. Int. Ed. 2009, 48, 3418. (d) Therrien, B.
Eur. J. Inorg. Chem. 2009, 2445. (e) Severin, K. Chem. Commun. 2006,
3859.
Entry
1
substrate
additiveb
−
yield [%]c
3: 80
1
2
3
4
5
6
7
8
benzaldehyde + 2a
4a: 13
3: 94
(3) Selected examples include: (a) Han, Y.-F.; Jin, G.-X.; Hahn, F. E. J.
Am. Chem. Soc. 2013, 135, 9263; (b) Riddell, I. A.; Smulders, M. M. J.;
Clegg, J. K.; Hristova, Y. R.; Breiner, B.; Thoburn, J. D.; Nitschke, J. R.
Nature Chem. 2012, 4, 751; (c) Conrady, F. M.; Fröhlich, R.; Brinke, C.
S.; Pape, T.; Hahn, F. E. J. Am. Chem. Soc. 2011, 133, 11496; (d) Han,
Y.-F.; Jia, W.-G.; Lin, Y.-J.; Jin, G.-X. Angew. Chem. Int. Ed. 2009, 48,
6234; (e) Therrien, B.; Süss-Fink, G.; Govindaswamy, P.; Renfrew, A.
K.; Dyson, P. J. Angew. Chem. Int. Ed. 2008, 47, 3773; (f) Shan, N.;
Vickers, S. J.; Adams, H.; Ward, M. D.; Thomas, J. A. Angew. Chem.
Int. Ed. 2004, 43, 3938; (g) Lehaire, M.-L.; Scopelliti, R.; Piotrowski,
H.; Severin, K. Angew. Chem. Int. Ed. 2002, 41, 1419.
2
3
4
benzaldehyde + 2a
benzaldehyde + 2b
benzaldehyde + 2c
benzonitrile
benzonitrile
benzonitrile
4a: trace
3: 92
4b: 11
3: 89
9
4c: 24
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
a Reaction conditions: aldehyde (0.5 mmol), catalyst (0.005 mmol)
in CH3NO2:MeOH (2:3). 0.5 mmol. Determined by GC analysis
using naphthalene or methylbenzene as internal standard.
b
c
(4) Wiester, M. J.; Ulmann, P. A.; Mirkin, C. A. Angew. Chem., Int. Ed.
2011, 50, 114.
(5) (a) Zhu, C.; Yuan, G.; Chen, X.; Yang, Z.; Cui, Y. J. Am. Chem. Soc.
2012, 134, 8058. (b) Farha, O. K.; Shultz, A. M.; Sarjeant, A. A.; Ngu-
yen, S. T.; Hupp, J. T. J. Am. Chem. Soc. 2011, 133, 5652. (c) Das, M. C.;
Xiang, S.; Zhang, Z.; Chen, B. Angew. Chem., Int. Ed. 2011, 50, 10510.
(d) Halper, S. R.; Do, L.; Stork, J. R.; Cohen, S. R. J. Am. Chem. Soc.
2006, 128, 15255.
In conclusion, we have developed a chelation-directed self-
sorting strategy to efficiently construct a series of heterome-
tallic metal-organic cages. The strategy can be applied to
different transition metals as the second site, such as copper,
nickel and zinc. Interesting metal-anchoring host-guest be-
havior was observed inside the HCCs. An in-cage size-
selective catalytic procedure was found for [HCC-1][OTf]8.
We believe that our synthetic strategy can allow us to devel-
op a larger HCC family with increased structural complexity
and controllability to provide better candidates for enzyme-
mimicking (biomimetic) catalysis. We are currently trying to
control the cage-refined environment of the active sites by
ligand modification.
(6) (a) Lee, S. J.; Cho, S.-H.; Mulfort, K. L.; Tiede, D. M.; Hupp, J. T.;
Nguyen, S. T. J. Am. Chem. Soc. 2008, 130, 16828. (b) Masar, M. S. III;
Gianneschi, N. C.; Oliveri, C. G.; Stern, C. L.; Nguyen, S. T.; Mirkin, C.
A. J. Am. Chem. Soc. 2007, 129, 10149.
(7) Examples include: (a) Smulders, M. M.; Jiménez, A.; Nitschke, J. R.
Angew. Chem., Int. Ed. 2012, 51, 6681. (b) Wu, H.-B.; Wang, Q.-M.
Angew. Chem., Int. Ed. 2009, 48, 7343. (c) de Wolf, P.; Waywell, P.;
Hanson, M.; Heath, S. L.; Meijer, A. J. H. M.; Teat, S. J.; Thomas, J. A.
Chem. Eur. J. 2006, 12, 2188. (d) Sun, S.-S.; Stern, C. L.; Nguyen, S. T.;
Hupp, J. T. J. Am. Chem. Soc. 2004, 126, 6314. (e) Sun, X.; Johnson, D.
W.; Caulder, D. L.; Raymond, K. N.; Wong, E. H. J. Am. Chem. Soc.
2001, 123, 2752.
ASSOCIATED CONTENT
Supporting Information
Experimental procedures, characterization data, catalytic study, mechanis-
tic study, kinetic investigation and crystallographic data for [HCC-
1][OTf]8, [HCC-2][OTf]8, {AgOTf
[HCC-6][OTf]8} and {pyrazine ⊂ [HCC-5][OTf]8} (in CIF format). This
(7) (a) Lee, S. J.; Cho, S.-H.; Mulfort, K. L.; Tiede, D. M.; Hupp, J. T.;
Nguyen, S. T. J. Am. Chem. Soc. 2008, 130, 16828. (b) Merlau, M. L.;
del Pilar Mejia, M.; Nguyen, S. T.; Hupp, J. T. Angew. Chem. Int. Ed.
2001, 40, 4239.
⊂ [HCC-1][OTf]8}, {AgOTf ⊂
(8) Huang, S.-L.; Lin, Y.-J.; Hor, T. S. A.; Jin, G.-X. J. Am. Chem. Soc.
2013, 135, 8125.
AUTHOR INFORMATION
(9) Han, Y.-F.; Jia, W.-G.; Yu, W.-B.; Jin, G.-X. Chem. Soc. Rev. 2009,
38, 3419 and references therein.
Corresponding Author
(10) Apart from our group’s work, similar interlocking structures
were also reported using long bridging ligands: Vajpayee, V.; Song, Y.
H.; Cook, T. R.; Kim, H.; Lee, Y.; Stang P. J.; Chi, K. W. J. Am. Chem.
Soc. 2011, 133, 19646.
Notes
The authors declare no competing financial interests.
(11) (a) Pardo, E.; Faus, J.; Julve, M.; Lloret, F.; Muñoz, M. C.; Cano, J.;
Ottenwaelder, X.; Journaux, Y.; Carrasco, R.; Blay, G.; Fernández, I.;
Ruiz-García, R. J. Am. Chem. Soc. 2003, 125, 10770. (b) Sönmez, M.;
Çelebı, M.; Leventa, A.; Berberb, İ.; Şentürka, Z. J. Coord. Chem. 2010,
63, 848.
ACKNOWLEDGMENT
This work was supported by the National Science Foundation of China
(91122017, 21374019), the Shanghai Science and Technology Committee
(13JC1400600, 13DZ2275200) and the Program for Changjiang Scholars
and Innovative Research Team in University (IRT1117).
(12) (a) Letko, C. S.; Heiden, Z. M.; Rauchfuss, T. B.; Wilson, S. R.
Inorg. Chem. 2011, 50, 5558. (b) Heiden, Z. M.; Gorecki, B. J.; Rauch-
fuss, T. B. Organometallics 2008, 27, 1542. (c) Miessler, G. L.; Tarr, D.
A. Inorganic Chemistry, 2nd ed.; Prentice-Hall, 1999.
REFERENCES
(1) For reviews of coordination-driven self-assembly, see: (a) Cook, T.
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Vajpayee, V.; Lee, M. H.; Stang, P. J.; Chi K.-W. Acc. Chem.
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Leininger, S.; Olenyuk, B.; Stang, P. J. Chem. Rev. 2000, 100, 853. (h)
Stang, P. J.; Olenyuk, B. Acc. Chem. Res. 1997, 30, 502.
(13) (a) Li, H.; Han, Y.-F.; Jin, G.-X. Dalton Trans. 2011, 40, 4982. (b)
Han, Y.-F.; Lin, Y.-J.; Jia, W.-G.; Jin, G.-X. Organometallics 2008, 27,
4088.
(14) In our previous research, we have found an example of unex-
pected metallomacrocycles using non-coplanar bridging ligands:
Wang, G.-L.; Lin Y.-J.; Berke, H.; Jin, G.-X. Inorg. Chem. 2010, 49,
2193.
(15) A similar effect in a multi-Lewis-acid complex can be seen in:
Futatsugi K.; Yamamoto, H. Angew. Chem., Int. Ed. 2005, 44, 1484.
(2) For reviews of application-oriented structure manipulation, see:
(a) Li, S.; Huang, J.; Cook, T. R.; Pollock, J. B.; Kim, H.; Chi, K.-W.;
Stang, P. J. J. Am. Chem. Soc. 2013, 135, 2084. (b) Han, Y.-F.; Li, H.; Jin,
G.-X. Chem. Commun. 2010, 46, 6879. (c) Yoshizawa, M.; Klosterman,
(16) Detailed mechanistic and kinetic investigations are described in
the Supporting Information.
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