A covalently-linked microporous organic-inorganic hybrid framework containing polyhedral oligomeric silsesquioxane moieties

Abstract

By a Yamamoto-type of Ullmann cross-coupling reaction, a well-defined covalently-linked microporous organic-inorganic hybrid framework polyoctaphenylsilsesquioxane (JUC-Z1) was effectively prepared from the nano building block p-iodio-octaphenylsilsesquioxane (I8OPS) with a yield of ca. 100%. The structure of JUC-Z1 was characterized by (13)C CP/MAS NMR and (29)Si MAS NMR experiments. Fourier transform infrared spectroscopy (FTIR) was performed to confirm the presence of functions in the framework. The results showed that inorganic silsesquioxane cubes were linearly covalently-linked by biphenyls, offering a highly cross-coupling framework. The powder X-ray diffraction (PXRD) pattern and transmission electron microscope (TEM) image show that JUC-Z1 is spherical with uniform micropores. N(2) adsorption results suggest that the hybrid framework has a narrow pore size distribution from 11.8 to 20.0 Å, with a BET surface area of 283 m(2)g(-1) and a pore volume of 0.226 cm(3)g(-1). A thermogravimetric (TG) analysis indicates the thermal stability of JUC-Z1 up to 397 °C in air. Moreover, a liquid sorption experiment reveals the favorable sorption of benzene and water.

An Efficient Approach to Octabromophenylethyl‐Functionalized Cage Silsesquioxane and Its Use in Constructing Hybrid Porous Materials

“…The hybrid porous polymers exhibit apparent BET surface areas and pore volumes that are comparable to those of other SQ-based porous polymers. [11,38] Figure 3. Nitrogen adsorption-desorption isotherms and the poresize distribution calculated by the nonlocal DFT approach (inset) of cage polymer 1 (Filled and empty symbols denote adsorption and desorption branches).…”

“…[10] Second, an efficient polymerization process should be selected to link those monomers together over a broad scale range. Many hybrid porous materials based on specific monomers have been reported, and they have been obtained by various polymerization reactions, such as the Ullmann cross-coupling reaction, [11] Sonogashira-Hagihara coupling reaction, [12] Suzuki coupling reaction, [13] Heck reaction, [14] Friedel-Crafts reaction, [15] and others. [16] These two key issues can provide a straightforward strategy to obtain porous polymers.…”

Storage of hydrogen, methane, carbon dioxide in electron-rich porous aromatic framework (JUC-Z2)

“…organic frameworks (POFs) such as metal-organic frameworks (MOFs) (Yaghi et al 2003;Mulfort et al 2010;Salles et al 2010;Sumida et al 2012;Guo et al 2011), covalent organic frameworks (COFs) (Côté et al 2005;El-Kaderi et al 2007;Wan et al 2008Wan et al , 2009Mohanty et al 2011), conjugated microporous polymers (CMPs) (Jiang et al 2007;Chen et al 2010;Dawson et al 2011;Li et al 2010), polymers of intrinsic microporosity (PIMs) (McKeown et al 2005;McKeown and Budd 2006;Ghanem et al 2010), hyper-crosslinked polymers (HCPs) Tsyurupa and Davankov 2002;Germain et al 2007), and porous aromatic frameworks (PAFs) (Ben et al 2009(Ben et al , 2011a(Ben et al , 2011bPeng et al 2011;Ren et al 2010;Lu et al 2011) have been synthesized and their application in gas storage, catalysis, molecular recognition were explored Trewin et al 2008;Alam and Mokaya 2010). The first gas sorption method to detect the pore structure of POFs was established by Yaghi et al andWilliams et al in 1998 and1999 by Langmuir and Brunauer-Emmett-Teller (BET) theory respectively, which was proved to be a standard of characterization of porosity of microporous organic frameworks (Eddaoudi et al 1998;Chui et al 1999).…”

Amphiphilic Organic–Inorganic Hybrid Zeotype Aluminosilicate like a Nanoporous Crystallized Langmuir–Blodgett Film

“…[4] Also,s everal covalently linked nanoporous materials having zeolite topology,f or example,J UC-Z1 [5] (LTA-type) and PSN-1 [6] (ACO-type), were synthesized by means of ac ross-coupling reaction. Besides,o rganicinorganic hybrid porous materials can be prepared from various layered silicates or clay minerals [7][8][9][10] and their structures are formed by employing al arge bulky organic molecule like an organosilane as apillar unit in the interlayer space.R ecently,B ellussi and co-workers have developed as eries of original crystalline aluminosilicates called ECS using ap henylene-bridged bis(triethoxysilyl)benzene (BTEB), some of which showed microporosity.…”