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Axial Ligand exchange in chiral macrocyclic ytterbium(III) complexes.

We investigate the role of axial ligands on the near-IR-optical and paramagnetic NMR spectra of the complex [YbL](+3) where L is the stereodefined enantiopure chiral macrocycle (L = hexaazapentacyclo[25.3.1.1(12,24).0(4,9).0(19,24)]dotriaconta-1(31),2,10,12,14,16(32),17,25,27,29-decaene). The conformation in solution of the lanthanide complex is characterized by analyzing the pseudocontact 1H NMR shifts and is consistent with X-ray data of single crystal of analogue systems. The macrocycle is confined within a thin equatorial disk, leaving the cation open to at least two axial sites, on the opposite hemispheres. We recorded, assigned, and analyzed the 1H NMR spectra of several species upon changing the anion in solution, calculating the magnetic susceptibility anisotropy tensor for each. Near-IR circular dichroism is used to investigate the solution equilibria involving the competing ligands and to derive a spectroscopic series for Yb.