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Black plate (232,1) 2. ‘‘Ship-in-a-bottle’’ complexes in zeolites The mystery of a ‘‘ship-in-a-bottle’’ languishes among the many shattered illusions of adults who learn beyond childhood that the essential framework components of the ship–mast and all–are first brought together and assembled inside the bottle, and finally the mast is ‘‘pulled-up’’ from outside as a pie`ce de re ́sistance thus presenting the full glory of the final vessel, apparently too big to fit through the bottle’s narrow neck. In a reasonable analogy, relatively large molecules may be assembled inside the supercages of zeolites from condensation and coordination reactions of smaller adsorbed species. There are various reports of potentially useful materials created using ship-in-a-bottle methods. For instance, the prefluor- escent probe dansyl-TEMPO (DT) was produced within the super- cages of NaY by means of a base-catalysed reaction to yield the supramolecular assembly DT@NaY, which is furthermore the first example of base-catalysed reaction within a zeolite. [The termi- nology A@X means that A is the encapsulated species while X is the zeolite concerned.] This material was successfully used as a solid state sensor to monitor the intercavity diffusion of carbon- centred radicals produced by AIBN thermolysis and in a slurry to study the inter-pore diffusion of carbon-centred radicals produced in solution from a 3,3 0 -diphenyl-3H,3 0 H-[3,3 0 ]bibenzofuranyl-2,2 0 - dione. The dynamics of hydrogen atom transfer from a good donor, such as the synthetic antioxidant 3-phenyl-2-coumaranone, to DT@NaY were also investigated in a benzene slurry12. 3- Hydroxyflavone (3-HOF) was incorporated in zeolite micropores by ship-in-a-bottle synthesis. 3-HOF molecules were found to exhibit excited-state intramolecular proton transfer and a tautomeric equilibrium was observed between the 3-HOF-excited structures N* and T*. The position of equilibrium is affected strongly by the protonic nature and polarity of the surrounding medium. The physical and spectroscopic characterization of the dye-loaded zeolite colloids enabled a correlation to be established between the optical properties of the dye and the environment of the zeolite micropores13. The 2,4,6-triphenylthiapyrylium cation was encapsu- lated in the supercages of the 3-dimensional large pore zeolites Y and beta via ship-in-a-bottle synthesis from chalcone and acetophe- none, in the presence of hydrogen sulfide. The resulting solids furnish efficient and robust photo-catalysts that can degrade phenol and aniline in water with a higher efficiency than the standard P-25 TiO2 catalyst can. There is further evidence that these encapsulated dye materials may also be efficient photo-catalysts for the oxidative 232 Christopher J. RhodesPDF Image | Properties and applications of zeolites
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