Published on Web 06/10/2010
CMPs as Scaffolds for Constructing Porous Catalytic
Frameworks: A Built-in Heterogeneous Catalyst with High
Activity and Selectivity Based on Nanoporous
Metalloporphyrin Polymers
Long Chen,†,§ Yong Yang,†,§ and Donglin Jiang*,†,‡
Department of Materials Molecular Science, Institute for Molecular Science, 5-1 Higashiyama,
Myodaiji, Okazaki 444-8787, Japan and PRESTO, JST, Japan
Received April 5, 2010; E-mail: jiang@ims.ac.jp
Abstract: This article describes the synthesis and functions of a porous catalytic framework based on
conjugated micro- and mesoporous polymers with metalloporphyrin building blocks (FeP-CMP). FeP-CMP
was newly synthesized via a Suzuki polycondensation reaction and was developed as a heterogeneous
catalyst for the activation of molecular oxygen to convert sulfide to sulfoxide under ambient temperature
and pressure. FeP-CMP is intriguing because the polymer skeleton itself is built from catalytic moieties
and serves as built-in catalysts, bears inherent open nanometer-scale pores that are accessible for
substrates, and possesses large surface areas (1270 m2 g-1) that facilitate the transformation reaction. It
is highly efficient with high conversion (up to 99%) and a large turnover number (TON ) 97,320), is widely
applicable to various sulfides covering from aromatic to alkyl and cyclic substrates, displays high selectivity
(up to 99%) to form corresponding sulfoxides, and is highly chemoselective for the oxidation of a sulfide
group even in the coexistence of other oxidative functionalities. Owing to the covalent linkages between
catalytic sites in the frameworks, FeP-CMP can be recycled with good retention of its porous structure and
allows for large-scale transformation. These unique characteristics clearly originate from the covalent porous
catalytic framework structure and demonstrate the usefulness of CMPs in the exploration of built-in
heterogeneous catalysts, a new potential of these materials that have thus far been reported to exhibit
noteworthy gas adsorption functions.
have successfully demonstrated their utility for gas adsorption.1-5
Recently, CMPs have been developed to load metal nanoclusters
Introduction
Conjugated micro- and mesoporous polymers (CMPs) are a
new class of porous materials with an amorphous organic
framework.1-5 CMPs are unique owing to their high flexibility
in the molecular design of components and the control of pore
parameters. Systematic studies on the porous structures of CMPs
for the synthesis of heterogeneous catalysts.2i,3f,g,4d Because the
polymer skeleton does not incorporate any catalytic sites, post-
(3) (a) Kuhn, P.; Antonietti, M.; Thomas, A. Angew. Chem., Int. Ed. 2008,
47, 3450–3453. (b) Kuhn, P.; Forget, A.; Su, D.; Thomas, A.;
Antonietti, M. J. Am. Chem. Soc. 2008, 130, 13333–13337. (c) Kuhn,
P.; Thomas, A.; Antonietti, M. Macromolecules 2009, 42, 319–326.
(d) Weber, J.; Thomas, A. J. Am. Chem. Soc. 2008, 130, 6334–6335.
(e) Schmidt, J.; Werner, M.; Thomas, A. Macromolecules 2009, 42,
4426–4429. (f) Schmidt, J.; Weber, J.; Epping, J. D.; Antonietti, M.;
Thomas, A. AdV. Mater. 2009, 21, 702–705. (g) Chan-Thaw, C. E.;
Villa, A.; Katekomol, P.; Su, D.; Thomas, A.; Prati, L. Nano Lett.
2010, 10, 537–541. (h) Wang, Y.; Zhang, J.; Wang, X.; Antonietti,
M.; Li, H. Angew. Chem., Int. Ed. 2010, 49, 3356–3359. (i) Palkovits,
R.; Antonietti, M.; Kuhn, P.; Thomas, A.; Schu¨th, F. Angew. Chem.,
Int. Ed. 2009, 48, 6909–6912.
† Institute for Molecular Science.
‡ JST.
§ These authors contributed equally.
(1) (a) Cooper, A. I. AdV. Mater. 2009, 21, 1291–1295. (b) Thomas, A.;
Kuhn, P.; Weber, J.; Titirici, M.-M.; Antonietti, M. Macromol. Rapid
Commun. 2009, 30, 221–236.
(2) (a) Jiang, J. X.; Su, F.; Trewin, A.; Wood, C. D.; Campbell, N. L.;
Niu, H.; Dickinson, C.; Ganin, A. Y.; Rosseinsky, M. J.; Khimyak,
Y. Z.; Cooper, A. I. Angew. Chem., Int. Ed. 2007, 46, 8574–8578. (b)
Jiang, J. X.; Su, F.; Trewin, A.; Wood, C. D.; Niu, H.; Jones, T. A.;
Khimyak, Y. Z.; Cooper, A. I. J. Am. Chem. Soc. 2008, 130, 7710–
7720. (c) Jiang, J. X.; Su, F.; Niu, H.; Wood, C. D.; Campbell, N. L.;
Khimyak, Y. Z.; Cooper, A. I. Chem. Commun. 2008, 486–488. (d)
Dawson, R.; Su, F.; Niu, H.; Wood, C. D.; Jones, J. T. A.; Khimyak,
Y. Z.; Cooper, A. I. Macromolecules 2008, 41, 1591–1593. (e) Sto¨ckel,
E.; Wu, X.; Trewin, A.; Wood, C. D.; Clowes, R.; Campbell, N. L.;
Jones, J. T. A.; Khimyak, Y. Z.; Adams, D. J.; Cooper, A. I. Chem.
Commun. 2009, 212–214. (f) Jiang, J. X.; Trewin, A.; Su, F.; Wood,
C. D.; Niu, H.; Jones, J. T. A.; Khimyak, Y. Z.; Cooper, A. I.
Macromolecules 2009, 42, 2658–2666. (g) Dawson, R.; Laybourn,
A.; Clowes, R.; Khimyak, Y. Z.; Adams, D. J.; Cooper, A. I.
Macromolecules 2009, 42, 8809–8816. (h) Trewin, A.; Cooper, A. I.
Angew. Chem., Int. Ed. 2010, 49, 1533–1535. (i) Hasell, T.; Wood,
C. D.; Clowes, R.; Jones, J. T. A.; Khimyak, Y. Z.; Adams, D. J.;
Cooper, A. I. Chem. Mater. 2010, 22, 557–564.
(4) (a) Schwab, M. G.; Fassbender, B.; Spiess, H. W.; Thomas, A.; Feng,
X.; Mu¨llen, K. J. Am. Chem. Soc. 2009, 131, 7216–7217. (b) Feng,
X.; Liang, Y.; Zhi, L.; Thomas, A.; Wu, D.; Lieberwirth, I.; Kolb,
U.; Mu¨llen, K. AdV. Funct. Mater. 2009, 19, 2125–2129. (c) Rose,
M.; Bohlmann, W.; Sabo, M.; Kaskel, S. Chem. Commun. 2008, 2462–
2464. (d) Feng, X.; Liang, Y.; Zhi, L.; Thomas, A.; Wu, D.;
Lieberwirth, I.; Kolb, U.; Mu¨llen, K. AdV. Funct. Mater. 2009, 19,
2125–2129. (e) Zhang, Y.; Riduan, S. N.; Ying, J. Y. Chem.sEur. J.
2009, 15, 1077–1081. (f) Farha, O. K.; Spokoyny, A. M.; Hauser,
B. G.; Bae, Y.-S.; Brown, S. E.; Snurr, R. Q.; Mirkin, C. A.; Hupp,
J. T. Chem. Mater. 2009, 21, 3033–3035. (g) Du, X.; Sun, Y.; Tan,
B.; Teng, Q.; Yao, X.; Su, C.; Wang, W. Chem. Commun. 2010, 46,
970–972. (h) Ben, T.; Rao, H.; Ma, S.; Cao, D.; Lan, J.; Jing, X.;
Wang, W.; Xu, J.; Deng, F.; Simmons, J. M.; Qiu, S.; Zhu, G. Angew.
Chem., Int. Ed. 2009, 48, 9457–9460.
9
9138 J. AM. CHEM. SOC. 2010, 132, 9138–9143
10.1021/ja1028556 2010 American Chemical Society