DFT-optimized structures of (a) [(Bn-TPEN)MnIV(O)]2+ (1), (b) [(Bn-TPEN)MnIV(O)–Sc(OTf)3]2+, and (c) [(Bn-TPEN)-MnIV(O)–[Sc(OTf)3]2]2+, calculated at the B3LYP/LACVP level in the solvent phase. The Mn–O bond lengths of [MnIV(O)]2+, [MnIV(O)]2+–Sc3+, and [MnIV(O)]2+–(Sc3+)2 were calculated to be 1.68, 1.75, and 1.75 Å, respectively (see the DFT Calculations Section in the the SI for computational details). H atoms in Bn-TPEN and F atoms in the OTf-counterions have been omitted for clarity (Mn, pink; N, blue; O, red; C, green; Sc, purple; S, yellow). (d) Schematic drawing of the Bn-TPEN ligand.