ABSTRACT
The dodecavanadate framework, [V12O32]4-, exhibits a unique bowl-type structure with an open molecular oxide cage having a cavity diameter of 4.4 Å, and different synthetic paths were required to construct the bowl-type structure with a different guest. A new dodecavanadate, {(n-C4H9)4N}4[V12O32(CH3NO2)] (1), is synthesized with a nitromethane guest, which is stacked above the entrance of the hemisphere rather than fully occupying the cavity, and it enables a guest-capturing reaction, while retaining the anionic cage structure. Compound 1 is a good precursor for halide-centered dodecavanadates, {(C2H5)4N}5[V12O32(X)] (X = Cl- (2), Br- (3), and I- (4)). The position of the halide inside the cavity correlates with the ionic radius of the guest; the small chloride ion sat at the far bottom, and the large iodide floated at the entrance. The inclusion reaction rates were estimated through 51V NMR time-course measurements in nitromethane. The reaction rates increase in the order I- < Br- < Cl-.
