The concept of carrying reactions in confined and organized media has gained significance in recent past.

It is being observed that encapsulation of a molecule into a nanocage activates the molecule, as well as the cage1. This technique is mostly applicable in performing catalysis e.g. CO oxidation by Fe in BN-Fullerene cage (1), C-H bond activation in a [Ga4L6] 12+ cluster (2).

Recently a group of researchers did catalytic hydration of epoxide in a silica-based nanoreactor in mild condition and they also got higher selectivity and activity of the catalyst. The reason behind the enhanced reactivity of a catalyst inside the cage can be attributed to the increase in local concentration of the catalyst inside the cage than in solution, i.e. homogeneous phase. It is being reported that Co content in the solid catalyst (catalyst+ cage) is 0.642 wt%. It is possible that the molecular catalysts get adsorbed onto the inner surface of the pore (Fig-1). More number of catalysts is now present in each pore to act on a single substrate, for which the catalyst becomes more reactive. During homogeneous catalysis, the reactivity of the catalyst molecules decreases in course of time due to self-degradation of catalyst molecules. When they are adsorbed on the surface the rate of degradation will be much diminished. It is being observed that the surface areas of FDU-12 and FDU-12- Co catalyst are respectively 740 and 100 m2/g. From this data it is quite evident that the catalyst molecules are adsorbed onto the inner surface of the pore. If the catalyst molecules were moving freely within the pore all the time the surface area would not be diminished so much. Now the chemical nature of the silica-based nanopore can be scrutinized by 29Si NMR spectroscopy done in solid state only. If solution state spectroscopy is performed there is a chance that the host-guest attachment would be effected and the catalysts will get some mobility in presence of added solvent and the true chemical nature of the silica pore cannot be well-explored. Chemical shifts of FDU-12, FDU-12- Co catalyst and FDU-12-Co catalyst-ethylene oxide would be recorded. If the encapsulated catalysts get adsorbed on the surface of the pore the value should be different for the 1st two systems but remain same for the last pair of systems. After the adsorption of the catalyst onto the Si-pore the value should be highly upfield (~ -28ppm) as the Si nuclei become highly shielded due to interaction with the transition metal. The Powder X-ray diffraction pattern of FDU-12-Co-catalyst would be different than that of pure FDU-12 if the catalysts are adsorbed onto the surface of the pore.

On suspension of the catalytic system in a solvent in which the catalyst is soluble, if the catalysts do not come out in the solution (which we can check from UV-Vis study of the solution and it should correspond to CoIII) that will also support the adsorption of the catalysts onto the pore surface. Hence by performing these simple experiments and studies the true nature of host-guest interaction can be deciphered and the proper reason behind this Cage Effect can be proposed.

References:
1. 2. 3. 4. Nigam, Majumdar, ACS NANO,2008, 2, 1422-1428 Bergman, Raymond, Angew. Chem. Int. Ed.,2004, 43, 963-966 Yang, Li, Energy Environ. Sci., 2012, 5, 8229 Yang, Li, Angew. Chem. Int. Ed., 2012, 51, 11517-11521