Ship-in-a-Bottle Syntheses

Confinement inside a protected environment might contribute to complex stabilization, because the effect of the atmosphere (air, moisture, solvents, other reactants) will be minimized. This is particularly true for liquid-phase 

Once synthesized, the nature of the encaged complex needs to be confirmed by a combination of characterization techniques. Spectroscopies such as UV-vis, IR, and Raman can be very useful as the zeolite matrix does not usually obstruct the interesting zones of the spectra. The former is used to probe the metal, while the latter two are more ligand-based techniques. Results are usually compared to the pure, unsupported, complex. Solid-state NMR can also give precious information but with enriched samples or analyses of heteroatoms, electron paramagnetic resonance (EPR) spectroscopy has also been used, especially with Co(II) complexes. X-ray photoelectron spectroscopy 

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Figure 1. Ship-in-a-bottle synthesis of metal carbonyl clusters in NaY zeolite.

Ruthenium Tris-bypyridine/Zeolite-Y/Titanium Dioxide Nano-Assembly Ship-in-a-Bottle Synthesis and Applieation in Heterogeneous Photodegradation of 2,4-xylidine... 

The synthetic route followed in the encapsulation of [Ru(bpy)3] + in ZeoliteY is referred as ship-in-a-bottle synthesis due to non-extractability of the [Ru(bpy)3] complex, once encapsulation has taken place within the cages of the zeolite Y. Nanoparticles of TiO was then introduced through TiClj in ethylene glycol mixture under argon, with sintering at 200°C. A schematic diagram of the synthesis is shown in Fig. 16.1 [1]. 

Ship-in-a Bottle Synthesis and Application in Heterogeneous Photodegradation... 

Ship-in-a-Bottle Synthesis of Bimetallic Clusters in Zeolites... 

Ship-in-a-bottle" synthesis of netal complexes inside zeolite cages has gained growing attention for the purpose of obtaining the catalytically active precursors surrounded with configurationally constrained circumstances [3]. 

Fig. 15. Ship-in-a-bottle synthesis of the trityl cation 16 from 13CCU and benzene inside the HY supercage. (Reprinted with permission from Tao and Maciel (118). Copyright 1996 American Chemical Society.)...

Corma, A. and Garcia, H. (2004) Supramolecular host—guest systems in zeolites prepared by ship-in-a-bottle synthesis. Eur. J. Inorg. Chem., 1143. 

The formation of these dinuclear complexes can be impeded by entrapment of the Mn(BPY)22+ complexes in the structure of zeolite Y. Preferably, Mn(BPY)2+ is assembled via ship-in-a-bottle synthesis in zeohte Y, through BPY adsorption on a NaY zeolite partially exchanged with Mn2+. Because a single zeolite Y supercage can contain only one Mn(BPY)2+ complex, the formation of dinuclear complexes is impossible for steric reasons. The reaction of H2C>2 with the zeolite-entrapped Mn(BPY)2+ complex does not lead to the same vigorous peroxide decomposition as occurs in solution. Instead, H2O2 is heterolytically activated on the Mn complex with civ-bipyridine ligands to form a Mn(IV)=0 or Mn(V)=0 species. The latter is a... 

Metal phthalocyanines are easily synthesized by vapor-phase condensation of four molecules of dicyanobenzene in the presence of molecular sieves such as faujasites or A1PO-5 (123-126). This results in direct entrapment of the macrocycle inside the molecular sieve s channels and cages. There are also reports of ship-in-a-bottle synthesis of porphyrins in zeolites, but since porphyrin synthesis requires a mixture of pyrrole and an aldehyde instead of a single compound, porphyrin synthesis is a much less clean process than phthalocyanine preparation (127). Alternatively, soluble porphyrins or phthalocyanines can be added to the synthesis gel of, for example, zeolite X. This also results in entrapped complexes (128). 

The immobilization of Ru-phthalocyanines follows routes similar to those employed for the analogous Fe complexes. Particularly, the perfluorinated Ru phthalocyanines were immobilized in zeolites by ship-in-a-bottle synthesis or by template synthesis, or in MCMs after surface modification. The materials display extremely high activities for the oxygenation of paraffins with r-BuOOH as the oxidant (128,288). 

Each zeolite type can be easily obtained over a wide range of compositions directly by synthesis and/or after various post synthesis treatments. Moreover, various compounds can be introduced or even synthesized within the zeolite pores (ship in a bottle synthesis). This explains why zeolites can be used as acid, base, acid-base, redox and bifunctional catalysts, most of the applications being however in acid and in bifunctional catalysis. 

From the seminal work of Lunsford et al. in the early 1980s (DeWilde et al., 1980 Quayle and Lunsford, 1982), ship-in-a-bottle synthesis of metal complexes in the zeolite supercages, encapsulation of catalytically, optically, and/or electrochemically active species within micro- and mesoporous aluminosilicates, has received considerable attention (Alvaro et al., 2003). Site isolation of individual guest molecules, combined with shape and size restrictions imposed by the supercage steric limitations. 

Alvaro, M., Carbonell, E., Domenech, A., Fomes, V., Garcia, H., and Narayana, M. 2003. Ship-in-a-bottle synthesis of a large guest occupying two zeohte Y neighbour supercages. Characterization and photocatalytic activity of encapsulated bipyryhum ion. Chemical Physics-Physical Chemistry 4, 483-487. 

Casades, L, Constantine, M.S., Cardin, D., Garcia, H., Gilbert, A., and Marquez, F. 2000. Ship-in-a-Bottle synthesis and photochromism of spiropyrans encapsulated within zeolite Y supercages. Tetrahedron 5(>, 6951-6956. 

Transition metal complexes of phthalocyanine encaged in faujasite type zeolites have been reported as efficient catalysts in the oxidation of alkanes at room temperature and atmospheric pressure [6-13]. These catalysts constitute potential inorganic mimics of remarkable enzymes such as monooxygenase cytochrome P-450 which displays the ultimate in substrate selectivity. In these enzymes the active site is the metal ion and the protein orientates the incoming substrate relative to the active metal center. Zeolites can be used as host lattices of metal complexes [14, 15]. The cavities of the aluminosilicate framework can replace the protein terciary structure of natural enzymes, thus sieving and orientating the substrate in its approach to the active site. Such catalysts are constructed by the so-called ship in a bottle synthesis the metal phthalocyanine complexes are synthesized in situ within the supercages of the zeolite... 

Figure 2. Some examples of micro- and mesoporous materials as the template micro reactors for ship-in-a-bottle synthesis of metal clusters in micropores and mesoporous channels.

Figure 3. Pictorial illustration of ship-in-a-bottle synthesis of metal clusters, Rh6(CO)i6 assembled in NaY cages by the suecessive carbonylation of Rh ions using CO + H2O or CO + H2 as building blocks, which are introduced by the ion-exchange methods and gas admission.

Furthermore, Ichikawa et. al. recently extended the ship-in-a-bottle synthesis for some other metal elusters such as Ru3(CO)i2/NaY, H4Ru4(CO)i2/NaY,f ... 

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