Redox Potentials of Uranyl Ions in Macrocyclic Complexes: Quantifying the Role of Counter-Ions

Several uranyl ions strapped with Schiff-base ligands in the presence of redox-innocent metal ions are synthesized, and their reduction potentials are recently estimated. The change in Lewis acidity of the redox-innocent metal ions contributes to ∼60 mV/pK_a unit quantified which is intriguing. Upon increasing the Lewis acidity of metal ions, the number of triflate molecules found near the metal ions also increases whose contributions toward the redox potentials remain poorly understood and not quantified until now. Most importantly, to ease the computational burden, triflate anions are often neglected in quantum chemical models due to their larger size and weak coordination to metal ions. Herein, we have quantified and dissected the individual contributions that arise alone from Lewis acid metal ions and from triflate anions with electronic structure calculations. The triflate anion contributions are large, in particular, for divalent and trivalent anions that cannot be neglected. It was presumed to be innocent, but we here show that they can contribute more than 50% to the predicted redox potentials, suggesting that their vital role in the overall reduction processes cannot be neglected.