pubs.acs.org/cm Published on Web 11/16/2009 r 2009 American Chemical Society 5792 Chem. Mater. 2009, 21, 5792–5800 DOI:10.1021/cm902164t Ethenylene-Bridged Periodic Mesoporous Organosilicas: From E to Z Carl Vercaemst,* ,† Matthias Ide, † Paul V. Wiper, ‡ James T. A. Jones, ‡ Yaroslav Z. Khimyak, ‡ Francis Verpoort, † and Pascal Van Der Voort* ,† † Department of Inorganic and Physical Chemistry, Centre for Ordered Materials, Organometallics and Catalysis (COMOC), University of Ghent, Krijgslaan 281, Building S3, 9000 Ghent, Belgium and ‡ Department of Chemistry, University of Liverpool, Crown Street, Liverpool L69 72D, United Kingdom Received July 16, 2009. Revised Manuscript Received October 27, 2009 A novel class of periodic mesoporous organosilicas with E- and/or Z-configured ethenylene bridges was prepared under acidic conditions using the triblock copolymer Pluronic P123 as a structure directing agent. The isomeric configuration of the precursor has a drastic effect on the properties of the resulting PMO materials. The diastereoisomerically pure E-configured ethenylene bridged PMOs reveal higher structural ordering, narrower pore size distributions, and enhanced hydrothermal stability than their diastereoisomerically impure counterparts. These properties have been correlated with the molecular level structure of pore walls probed by solid-state NMR spectroscopy. Introduction With the discovery of ordered mesoporous M41S silica materials, synthesized by means of the liquid crystal templating method, a new era in the field of porous materials commenced. 1 Within the next decade, numer- ous publications on ordered mesoporous materials followed, concerning both the synthesis of novel ordered materials 2,3 and the development of various potential applications in catalysis, 4-6 adsorption chemistry, 7 chromatography, 8-10 environmental technology, 11-13 microelectronics, 14 drug delivery, 15 and sensing. 16-18 A very interesting breakthrough was the discovery of periodic mesoporous organosilicas (PMOs) in 1999. 3,19,20 These novel organic-inorganic hybrid composites are synthe- sized using bridged organosilanes, most commonly of the type (R 0 O) 3 Si-R-Si(OR 0 ) 3 , in the presence of a struc- ture-directing agent (SDA). They are a promising class of ordered materials that combine the structural features of ordered mesoporous silicas with the chemical functionality of organic groups. Doing so, they open up a wide range of new opportunities in designing materials with novel organic functionalities and controlled morphological, structural, and surface properties. To date, PMOs with various rigid organic functionalities have been synthesized, ranging from short aliphatic and aromatic groups such as methane, 21 ethane, 22 ethene, 3,23-27 benzene, 28-30 and xylene 31 to cyclic 32 *Corresponding author. E-mail: carl.vercaemst@ugent.be (C.V.); pascal. vandervoort@ugent.be (P.V.D.V). Fax: þ32 9264 4983. Tel: þ32 9264 4442. (1) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S. Nature 1992, 359, 710. (2) Zhao, D. Y.; Feng, J. L.; Huo, Q. S.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G. D. Science 1998, 279, 548. (3) Asefa, T.; MacLachan, M. J.; Coombs, N.; Ozin, G. A. Nature 1999, 402, 867. (4) Corma, A.; Das, D.; Garcia, H.; Leyva, A. J. Catal. 2005, 229, 322. (5) Corma, A.; Garcia, H. Adv. Synth. Catal. 2006, 348, 1391. (6) Taguchi, A.; Schuth, F. Microporous Mesoporous Mater. 2005, 77, 1. (7) Yoshitake, H.; Yokoi, T.; Tatsumi, T. Chem. Mater. 2002, 14, 4603. (8) Ma, Y. R.; Qi, L. M.; Ma, J. M.; Wu, Y. Q.; Liu, O.; Cheng, H. M. Colloids Surf., A 2003, 229, 1. (9) Martin, T.; Galarneau, A.; Di Renzo, F.; Brunel, D.; Fajula, F.; Heinisch, S.; Cretier, G.; Rocca, J. L. Chem. Mater. 2004, 16, 1725. (10) Nassivera, T.; Eklund, A. G.; Landry, C. C. J. Chromatogr., A 2002, 973, 97. (11) Fryxell, G. E.; Liu, J.; Hauser, T. A.; Nie, Z. M.; Ferris, K. F.; Mattigod, S.; Gong, M. L.; Hallen, R. T. Chem. Mater. 1999, 11, 2148. (12) Liu, A. M.; Hidajat, K.; Kawi, S.; Zhao, D. Y. Chem. Commun. 2000, 1145. (13) Zhang, L. X.; Zhang, W. H.; Shi, J. L.; Hua, Z.; Li, Y. S.; Yan, J. Chem. Commun. 2003, 210. (14) Wu, C. G.; Bein, T. Science 1994, 264, 1757. (15) Mal, N. K.; Fujiwara, M.; Tanaka, Y. Nature 2003, 421, 350. (16) Descalzo, A. B.; Jimenez, D.; Marcos, M. D.; Martinez-Manez, R.; Soto, J.; El Haskouri, J.; Guillem, C.; Beltran, D.; Amoros, P.; Borrachero, M. V. Adv. Mater. 2002, 14, 966. (17) Descalzo, A. B.; Rurack, K.; Weisshoff, H.; Martinez-Manez, R.; Marcos, M. D.; Amoros, P.; Hoffmann, K.; Soto, J. J. Am. Chem. Soc. 2005, 127, 184. (18) Johnson-White, B.; Zeinali, M.; Shaffer, K. M.; Patterson, C. H.; Charles, P. T.; Markowitz, M. A. Biosens. Bioelectron. 2007, 22, 1154. (19) Inagaki, S.; Guan, S.; Fukushima, Y.; Ohsuna, T.; Terasaki, O. J. Am. Chem. Soc. 1999, 121, 9611. (20) Melde, B. J.; Holland, B. T.; Blanford, C. F.; Stein, A. Chem. Mater. 1999, 11, 3302. (21) Asefa, T.; MacLachlan, M. J.; Grondey, H.; Coombs, N.; Ozin, G. A. Angew. Chem., Int. Ed. 2000, 39, 1808. (22) Sayari, A.; Yang, Y. Chem. Commun. 2002, 2582. (23) Vercaemst, C.; Friedrich, H.; de Jongh, P. E.; Neimark, A. V.; Goderis, B.; Verpoort, F.; Van Der Voort, P. J. Phys. Chem. C 2009, 113, 5556. (24) Vercaemst, C.; Ide, M.; Allaert, B.; Ledoux, N.; Verpoort, F.; Van der Voort, P. Chem. Commun. 2007, 2261. (25) Wang, W. H.; Xie, S. H.; Zhou, W. Z.; Sayari, A. Chem. Mater. 2004, 16, 1756. (26) Xia, Y. D.; Yang, Z. X.; Mokaya, R. Chem. Mater. 2006, 18, 1141. (27) Vercaemst, C.; de Jongh, P. E.; Meeldijk, J. D.; Goderis, B.; Verpoort, F.; Van Der Voort, P. Chem. Commun. 2009, 4052. (28) Inagaki, S.; Guan, S.; Ohsuna, T.; Terasaki, O. Nature 2002, 416, 304. (29) Kapoor, M. P.; Inagaki, S.; Ikeda, S.; Kakiuchi, K.; Suda, M.; Shimada, T. J. Am. Chem. Soc. 2005, 127, 8174. (30) Kuroki, M.; Asefa, T.; Whitnal, W.; Kruk, M.; Yoshina-Ishii, C.; Jaroniec, M.; Ozin, G. A. J. Am. Chem. Soc. 2002, 124, 13886. (31) Temtsin, G.; Asefa, T.; Bittner, S.; Ozin, G. A. J. Mater. Chem. 2001, 11, 3202. (32) Landskron, K.; Hatton, B. D.; Perovic, D. D.; Ozin, G. A. Science 2003, 302, 266.