Ytterbium and yttrium complexes of octadentate ligands based on 1,4,7,10-tetraazacyclododecane with a coordinated pyridyl group and either tricarboxylate (L-1) or triphosphinate (L-2) donors form twisted-square-antiprismatic structures. The former crystallizes in the centrosymmetric group P2(1)/c, with the two molecules related by an inversion center, whereas the latter was found as an unusual kryptoracemate in the chiral space group P2(1). Pure shift NMR and EXSY spectroscopy allowed the dynamic exchange between the (RRR)-Delta-(delta delta delta delta) and (RRR)-Lambda-(lambda lambda lambda lambda) TSAP diastereomers of the [Y.L-2] complex to be detected. The rate-limiting step in the exchange between Delta and Lambda isomers involves cooperative ligand arm rotation, which is much faster for [Ln.L-1 than for [Ln.L-2]. Detailed analysis of NOESY, COSY, HSQC, and HMBC spectra confirms that the major conformer in solution is (RRR)-Lambda-(lambda lambda lambda lambda), consistent with crystal structure analysis and DFT Calculations. The magnetic susceptibility tensors for [Yb.L-1] and [Yb.L-2], obtained from a full pseudocontact chemical shift analysis, are very different, in agreement with a CASSCF calculation. The remarkably different pseudocontact shift behavior is explained by the change in the orientation of the pseudocontact shift field, as defined by the Euler angles of the susceptibility tensor.