Occluded guest

For microporous compounds with special compositions, calcination effects are even more severe. As compared with zeolites, these compounds have lower thermal stability. Strictly speaking, most of them are nonporous since removal of the occluded guest molecules by calcination usually results in collapse. This is due to strong H-bonds with the framework, coordination bonds, and sometimes the templating molecule is shared with the inorganic polyhedra. Relevant examples of low-stability microporous compounds with interesting structural features are zeolitic open-framework phosphates made of Ga [178], In [179], Zn [180], Fe [181],... 

That crosslinking has indeed occurred is confirmed by the very existence of aggregates at 25 °C, as in its absence the diblock copolymers are completely soluble at this temperature. Tunability of the solubility of the PMEMA block in water arises from the fact that its lower critical solution temperature (LCST) lies between 25 and 60 °C. This reversible hydration of the core could be a very useful feature to trigger release of occluded guest molecules from the core interior. More recently, utilizing a similar methodology, zwitterionic shell-crosslinked systems have also been prepared wherein the core and shell domains contain amine and carboxylic acid groups, respectively, or vice versa. Such systems exhibit an isoelectric point, at a pH wherein the crosslinked micelles ( 40 nm) become electrically neutral and precipitate out in water addition of acid or base causes complete redissolution of these nanospheres [58]. 

Crystalline microporous silicas, the porosils, are a family of materials based on [TO4] units with tetrahedral densities below 21 T-atoms per 1000 A, which are synthesized in the presence of teinplating guest molecules. Their silica host frameworks are three-dimensionally four-connected, and in their calcined form, they belong to the large family of silica polymorphs. Porosils with pore openings too small to let the occluded guest molecules out are called clathrasils porosils in which the guests can be removed are called zeosils. 

Zeolites are porous aluminosilicates with cavities and channels which may contain occluded guests, often used for purification or deionisation. 

A different approach towards the incorporation of metal oxide clusters into zeo-litic pores via chemical vapor deposition has been studied extensively by Ozin et al. [236 - 240]. They developed a method denoted as intrazeolite metal carbonyl phototopotaxy . Metal carbonyls are used as precursors to obtain the occluded guest component because of their volatility, fitting molecular dimensions, ease of purification, ready availability, and facile and quantitative conversion to the respective metal oxide materials with minimal contamination by carbon [236, 240]. The metal carbonyl precursors are transformed into the metal oxides by photochemical oxidation. The term phototopotaxy is meant to indicate the similarity of this preparation method to epitactical growth of semiconducting oxide layers on planar surfaces commonly used to form low-dimensional quantum nanostructures for applications in electronic and optical devices [238]. 

The concept zeolites conventionally served as the synonym for aluminosilicates with microporous host lattice structures. Upon removal of the guest water, zeolites demonstrate adsorptive property at the molecular level as a result they are also referred to as molecular sieves. Crystalline zeosils, AlPO s, SAPO s, MAPO s (M=metal), expanded clay minerals and Werner compounds are also able to adsorb molecules vitally on reproval of any of the guest species they occlude and play an Important role in fields such as separation and catalysis (ref. 1). Inclusion compounds are another kind of crystalline materials with open framework structures. The guest molecules in an inclusion compound are believed to be indispensable to sustaining the framework structure their removal from the host lattice usually results in collapse of the host into a more compact crystal structure or even into an amorphous structure. 

The Mn(III) complex 31b was tested as a catalyst for the epoxidation of various alkenes using sodium hypochlorite or iodosylbenzene as oxidants. Although oxidation took place, no selectivity was observed. For example, allylresorcinol was not epoxidized with rates higher than that of allylbenzene. Presumably, the substrate is not bound in the cleft of 31b because the latter is occluded by methoxy groups. It is possible that the reaction occurs on the outside of the metalloclip, which cannot discriminate between guest molecules. 

Recent work by Rabo et al. (57) opens new possibilities for controlling the activity and selectivity of zeolite catalysts. Occlusion of various guest molecules into the sodalite cavities of Y zeolites can significantly change the catalytic properties of the zeolites for carbonium-type reactions. Anions of occluded salts are located close to the center of the sodalite cavity and strongly influence the arrangement of cations in the faujasite lattice and hence the catalytic activity. 

On a macroscopic basis, it is difficult to remove all excess water from the hydrate mass this causes a substantial decrease in the accuracy of hydrate composition measurements. Hydrate formations often occlude water within the solid in a metastable configuration, thereby invalidating the composition obtained upon dissociation. Mixed guest compositions of the hydrate are also confounded by the concentration of heavy components in the hydrate phase. Unless the associated gas reservoir is large, preferential hydration may result in variable gas consumption and perhaps an inhomogeneous hydrate phase as discussed in Chapter 6. 

Structure-Reactivity Relationship in Deoxycholic Acid Complexes.—The three-channel motifs offer a variety of host-guest arrangements that may be exploited for the performance of solid-state reactions. Two kinds of reagents were occluded (a) peroxides, hydroperoxides, and peresters, which were activated thermally or by irradiation, (b) ketones, which were activated photochemically. 

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