Playing with the Chaotropic Effect to Improve the Encapsulation of Decaborate Clusters within Cyclodextrins

Probing the Electronic Structure of [B10H10]2– Dianion Encapsulated by an Octamethylcalix[4]pyrrole Molecule

“…For superchaotropic closo -borate dianions, the stabilization from H 2 O molecules is quite limited. , On the other hand, the stabilization arising from a counterion is very strong and may shift lower-lying molecular orbitals (MOs) out of the measurable range . A moderate stabilization effect is often afforded by organic host molecules known to effectively encapsulate closo -borate dianions. − Furthermore, the stabilization from a large organic host molecule is usually more symmetric compared to that afforded by a solvent molecule or a counterion, thus avoiding the disturbance of the electronic structure of the ion under investigation. Such disturbance has become obvious in microsolvated [B 12 I 12 ] 2– , as well as the [KB 12 H 12 ] − ion pair (Figure S1), both exhibiting significantly broadened spectral profiles compared to the isolated species.…”