%0 Journal Article %A Mason, Kevin %A Rogers, Nicola J. %A Suturina, Elizaveta A. %A Kuprov, Ilya %A Aguilar, Juan A. %A Batsanov, Andrei S. %A Yufit, Dmitry S. %A Parker, David %D 2017 %T PARASHIFT Probes: Solution NMR and X‑ray Structural Studies of Macrocyclic Ytterbium and Yttrium Complexes %U https://acs.figshare.com/articles/journal_contribution/PARASHIFT_Probes_Solution_NMR_and_X_ray_Structural_Studies_of_Macrocyclic_Ytterbium_and_Yttrium_Complexes/4753720 %R 10.1021/acs.inorgchem.6b02291.s001 %2 https://ndownloader.figshare.com/files/7796716 %K yttrium complexes %K crystal structure analysis %K Pure shift NMR %K Solution NMR %K L 2 %K L 1 %K susceptibility tensors %K DFT calculations %K Yb.L 1 %K CASSCF calculation %K COSY %K HSQC %K chiral space group P 2 1 %K TSAP %K Macrocyclic Ytterbium %K Λ isomers %K rate-limiting step %K inversion center %K Ln.L 1 %K pseudocontact shift field %K RRR %K pseudocontact chemical shift analysis %K HMBC spectra %K pyridyl group %K ligand arm rotation %K EXSY spectroscopy %K susceptibility tensor %K donors form twisted-square-antiprismatic structures %K Euler angles %K PARASHIFT Probes %K octadentate ligands %K Yttrium Complexes Ytterbium %K NOESY %K pseudocontact shift behavior %K Y.L 2 %X Ytterbium and yttrium complexes of octadentate ligands based on 1,4,7,10-tetraazacyclododecane with a coordinated pyridyl group and either tricarboxylate (L1) or triphosphinate (L2) donors form twisted-square-antiprismatic structures. The former crystallizes in the centrosymmetric group P21/c, with the two molecules related by an inversion center, whereas the latter was found as an unusual kryptoracemate in the chiral space group P21. Pure shift NMR and EXSY spectroscopy allowed the dynamic exchange between the (RRR)-Δ-(δδδδ) and (RRR)-Λ-(λλλλ) TSAP diastereomers of the [Y.L2] complex to be detected. The rate-limiting step in the exchange between Δ and Λ isomers involves cooperative ligand arm rotation, which is much faster for [Ln.L1] than for [Ln.L2]. Detailed analysis of NOESY, COSY, HSQC, and HMBC spectra confirms that the major conformer in solution is (RRR)-Λ-(λλλλ), consistent with crystal structure analysis and DFT calculations. The magnetic susceptibility tensors for [Yb.L1] and [Yb.L2], 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. %I ACS Publications