The paramagnetic one-dimensional ¹H NMR spectra of twelve Ln^IIINa^I(OAc)₄[12-MC_Mn^III(N)shi-4] complexes, where Ln^III is Pr^III-Yb^III (except Pm^III) and Y^III, are reported. Their solid-state isostructural nature is confirmed in methanol-d₄ solution, as a similar pattern in the ¹H NMR spectra is observed along the series. Notably, a relatively well-resolved spectrum is reported for the Gd^III complex. The chemical shift data are analyzed using the "all lanthanides" method, and the Fermi contact and pseudo-contact contributions are calculated for the lanthanide-induced shift (LIS). For the Tb^III-Yb^III complexes, the pseudo-contact contributions are typically 1 order of magnitude higher than the Fermi contact contributions; however, for the Gd^III complex, the Fermi contact is the main contribution to the paramagnetic chemical shift. For the methyl protons of the axial acetate (^-OAc) ligands, the LIS is opposite in sign, with respect to that of the aromatic salicylhydroximate (shi^3-) protons, because of structural rearrangements that occur upon dissociation of the Na^I cation in solution. The calculated crystal field parameters (B_Ln) for the Tb^III (360 cm^-1), Dy^III (250 cm^-1), Ho^III (380 cm^-1), Er^III (410 cm^-1), Tm^III (620 cm^-1), and Yb^III (380 cm^-1) complexes are not constant, likely as a consequence of the inaccuracy of the Bleaney's constants and, to a smaller extent, the small structural changes that occur in solution. Overall, the metallacrown scaffold retains structural integrity and similarity in solution for the entire series; however, small structural features, which do not affect the overall similarity, do likely occur.

Vittoria Marzaroli

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