Endohedral isomerism in model achiral and chiral La@C₅₈N₂ systems

Endohedral structures with La⁰ or La³⁺ encapsulated in chiral (1,16)C₅₈N₂ or achiral (1,4)C₅₈N₂ diazafullerenes were studied at the B3LYP/G-31G*/SDD level. Two stable locations of La⁰ and La³⁺ are possible in each cage but only with La⁰@(1,16)C₅₈N₂ can the two isomers coexist. We found that an AIM determined hapticity of the endohedral species selectively differentiates the systems. We predict that there will always exist IR and Raman bands which allow for them to be identified in the presence of the parent cage. For the La⁰@(1,16) C₅₈N₂ molecules and the parent diazafullerene, the Raman spectra are likely to reveal a pre-resonance effect even at 785 nm and it seems possible to selectively excite only one isomer. The calculated electronic spectra suggested a chance to determine the less populated diazafullerene in the presence of the more populated one, be it chiral or achiral. For the chiral endohedral isomers, the calculated VCD spectra are quite dissimilar and the two endohedral isomers and the parent heterofullerene seem to be easily detected. Eventually, we defined the endohedral isomerism as follows: The endohedral isomerism is the phenomenon whereby an internal individuum captured in a cage can occupy more than one stable position without changing the cage connectivity.