Encapsulation Studies on closo-Dicarbadodecaborane Isomers in Neutral Tetrahedral Palladium(II) Cages

The encapsulation of icosahedral closo-dicarbadodecaborane (o-, m-, and p-carboranes, Cb) as guest molecules at the intrinsic cavities of the three isostructural tetrahedral cages [{Pd₃(NⁱPr)₃PO}₄(Cl-AN)₆] (1), [{Pd₃(NⁱPr)₃PO}₄(Br-AN)₆] (2), and [{Pd₃(NⁱPr)₃PO}₄(H-AN)₆] (3) was studied. The formation of definite host-guest assemblies was probed with mass spectrometry, IR, and NMR spectral analysis. 2D DOSY ¹H NMR of the Cb⊂Cage systems showed similar diffusion coefficient (D) values for the host and guest species, signifying the encapsulation of these guests inside the cage assemblies. The hydrodynamic radius (R_H) derived from the D values of the host and guest species further confirmed the encapsulation of the Cb isomers at the cage pockets. The single-molecule energy optimization of the host-guest assemblies indicated the preferential binding of o-Cb as a guest inside the cages (1-3). The stabilization of these Cb guests inside these cages was further attributed to various possible nonclassical C-H···X-type interactions.