Standard Redox Potentials of Fe(III) Aqua Complexes Included into the Cavities of Cucurbit[ n]urils ( n = 6-8): A DFT Forecast.

An approach for estimating at the DFT level of the standard redox potentials of the inclusion compounds based on Fe(III) and Fe(II) aqua complexes inside the cavities of cucurbit[ n]urils ( n = 6-8) has been proposed. These inclusion compounds were established to have compositions which can be described by the formulas [Fe(H2O)6]3+/2+@CB[6] and [Fe(H2O)6·4H2O]3+/2+@CB[7,8]. Redox potentials E0 relative to the standard hydrogen electrode for the half-reaction Fe(III)/Fe(II) in the CB[ n] cavities calculated at the PBE/TZVP level within the molecular-continuum solvation model are 1.607, 0.949, and 0.847 V for n = 6, 7, and 8, respectively. The obtained values indicate a relative increase of the oxidative ability of Fe(III) aqua-ions in the cavities of the examined CB[ n], especially in CB[6], compared to the calculated value ( E0 = 0.786 V) for the same half-reaction in the bulk of aqueous solution. Possible causes of the detected trend are discussed. The calculations also showed that the Fe(III) aqua complex inside the CB[6] changes its magnetic properties, transforming into a low-spin state with a total spin S = 1/2, whereas for all other systems high-spin states in accord with the classical ligand field theory are realized.