5 A. Corma, H. Garcia and F. X. Llabres i Xamena, Chem. Rev.,
2010, 110, 4606–4655.
6 G. Ferey, Chem. Soc. Rev., 2008, 37, 191–214.
7 K. P. Lillerud, U. Olsbye and M. Tilset, Top. Catal., 2010, 53,
859–868.
8 K. Schlichte, T. Kratzke and S. Kaskel, Microporous Mesoporous
Mater., 2004, 73, 81–88.
9 L. Alaerts, J. Wahlen, P. A. Jacobs and D. E. De Vos, Chem.
Commun., 2008, 1727–1737.
10 M. Tonigold, Y. Lu, B. Bredenkotter, B. Rieger, S. Bahnmuller,
J. Hitzbleck, G. Langstein and D. Volkmer, Angew. Chem., Int.
Ed., 2009, 48, 7546–7550.
11 P. Horcajada, S. Surble, C. Serre, D. Y. Hong, Y. K. Seo,
J. S. Chang, J. M. Greneche, I. Margiolaki and G. Ferey, Chem.
Commun., 2007, 2820–2822.
12 F. X. Llabres i Xamena, O. Casanova, R. G. Tailleur, H. Garcia
and A. Corma, J. Catal., 2008, 255, 220–227.
13 M. Sabo, A. Henschel, H. Froede, E. Klemm and S. Kaskel,
J. Mater. Chem., 2007, 17, 3827–3832.
14 G. Ferey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour,
S. Surble and I. Margiolaki, Science, 2005, 309, 2040–2042.
15 D. Y. Hong, Y. K. Hwang, C. Serre, G. Ferey and J. S. Chang, Adv.
Funct. Mater., 2009, 19, 1537–1552.
16 J. Juan-Alcaniz, E. V. Ramos-Fernandez, U. Lafont, J. Gascon
and F. Kapteijn, J. Catal., 2010, 269, 229–241.
17 N. V. Maksimchuk, K. A. Kovalenko, S. S. Arzumanov,
Y. A. Chesalov, M. S. Melgunov, A. G. Stepanov, V. P. Fedin
and O. A. Kholdeeva, Inorg. Chem., 2010, 49, 2920–2930.
18 S. R. Bajpe, C. E. A. Kirschhock, A. Aerts, E. Breynaert,
G. Absillis, T. N. Parac-Vogt, L. Giebeler and J. A. Martens,
Chem.–Eur. J., 2010, 16, 3926–3932.
19 S. Hermes, M. K. Schroter, R. Schmid, L. Khodeir, M. Muhler,
A. Tissler, R. W. Fischer and R. A. Fischer, Angew. Chem., Int. Ed.,
2005, 44, 6237–6241.
20 A. Henschel, K. Gedrich, R. Kraehnert and S. Kaskel, Chem.
Commun., 2008, 4192–4194.
Fig. 1 Tetralin conversion (solid line) and selectivity toward 1-tetralone
(dashed line) of homogeneous FePcF16 and RuPcF16 complexes (grey)
and FePcF16@MIL-101 (A) and RuPcF16@MIL-101 (B) (black) with
significantly lower catalyst contents (n(tetralin) : n(MPcF16)
=
147 000 : 1 (Fe) and 92 000 : 1 (Ru)) compared to the non-
incorporated complexes (36 000 : 1) explaining the clear difference in
turnover numbers (TONs) after 6 h and 24 h (inset), respectively.
21 M. H. Alkordi, Y. L. Liu, R. W. Larsen, J. F. Eubank and
M. Eddaoudi, J. Am. Chem. Soc., 2008, 130, 12639–12641.
22 S. Horike, S. Shimomura and S. Kitagawa, Nat. Chem., 2009, 1,
695–704.
23 R. Makiura, S. Motoyama, Y. Umemura, H. Yamanaka,
O. Sakata and H. Kitagawa, Nat. Mater., 2010, 9, 565–571.
24 I. M. Geraskin, M. W. Luedtke, H. M. Neu, V. N. Nemykin and
V. V. Zhdankin, Tetrahedron Lett., 2008, 49, 7410–7412.
25 A. B. Sorokin and E. V. Kudrik, Catal. Today, 2010, DOI: 10.1016/
j.cattod.2010.1006.1020.
26 A. B. Sorokin, E. V. Kudrik and D. Bouchu, Chem. Commun.,
2008, 2562–2564.
27 E. V. Kudrik and A. B. Sorokin, Chem.–Eur. J., 2008, 14,
7123–7126.
28 U. Isci, P. Afanasiev, J. M. M. Millet, E. V. Kudrik, V. Ahsen and
A. B. Sorokin, Dalton Trans., 2009, 7410–7420.
29 P. Afanasiev, D. Bouchu, E. V. Kudrik, J. M. M. Millet and
A. B. Sorokin, Dalton Trans., 2009, 9828–9836.
30 P. E. Ellis and J. E. Lyons, J. Chem. Soc., Chem. Commun., 1989,
1315–1316.
31 K. J. Balkus, Jr., A. G. Gabrielov, S. L. Bell, F. Bedioui, L. Roue
and J. Devynck, Inorg. Chem., 1994, 33, 67–72.
32 K. J. Balkus, M. Eissa and R. Levado, J. Am. Chem. Soc., 1995,
117, 10753–10754.
33 J. M. Thomas, R. Raja, G. Sankar and R. G. Bell, Nature, 1999,
398, 227–230.
34 A. B. Sorokin and A. Tuel, Catal. Today, 2000, 57, 45–59.
35 A. B. Sorokin, S. Mangematin and C. Pergrale, J. Mol. Catal. A:
Chem., 2002, 182–183, 267–281.
36 J. Kim, S. Bhattacharjee, K. E. Jeong, S. Y. Jeong and W. S. Ahn,
Chem. Commun., 2009, 3904–3906.
37 S. B. Lei, C. Wang, S. X. Yin, H. N. Wang, F. Xi, H. W. Liu, B. Xu,
L. J. Wan and C. L. Bai, J. Phys. Chem. B, 2001, 105, 10838–10841.
38 P. Horcajada, C. Serre, G. Maurin, N. A. Ramsahye, F. Balas,
M. Vallet-Regi, M. Sebban, F. Taulelle and G. Ferey, J. Am. Chem.
Soc., 2008, 130, 6774–6780.
should be operating in homogeneous and heterogeneous
systems. These low KIE values indicate the involvement of a
radical mechanism in this reaction. The occurrence of an
induction period and the detection of a small concentration of
tetralinhydroperoxide by GC-MS over the course of tetralin
oxidation are also consistent with a free radical mechanism of
oxidation, as previously suggested elsewhere.12
In summary, this study demonstrates that the encapsulation
of MPc in MIL-101 allows an activity increase of
approximately one order of magnitude. This increase in
activity may arise from the dispersion of the molecular
complexes as isolated monomers in the nanopore cavities
and/or from the confinement effects provided by the host
porous structure. In contrast, the (FePctBu4)2N dimer, which
is too large to penetrate into the porous structure, does not
show this synergistic effect.
We thank the ANR for financial support (ANR-08-
BLANC-0183-01).
Notes and references
1 U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt
and J. Pastre, J. Mater. Chem., 2006, 16, 626–636.
2 D. Farrusseng, S. Aguado and C. Pinel, Angew. Chem., Int. Ed.,
2009, 48, 7502–7513.
3 J. Y. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. B. T. Nguyen
and J. T. Hupp, Chem. Soc. Rev., 2009, 38, 1450–1459.
4 L. Q. Ma, C. Abney and W. B. Lin, Chem. Soc. Rev., 2009, 38,
1248–1256.
39 A. Sorokin, A. Robert and B. Meunier, J. Am. Chem. Soc., 1993,
115, 7293–7299.
c
1564 Chem. Commun., 2011, 47, 1562–1564
This journal is The Royal Society of Chemistry 2011