title: PARASHIFT Probes: Solution NMR and X-ray Structural Studies of Macrocyclic Ytterbium and Yttrium Complexes.
abstract: 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.
authors.affiliation: Department of Chemistry, Durham University , South Road, Durham DH1 3LE, U.K.
authors.forename: Kevin
authors.initials: K
authors.lastname: Mason
authors.affiliation: Department of Chemistry, Durham University , South Road, Durham DH1 3LE, U.K.
authors.forename: Nicola J
authors.identifier: http://orcid.org/0000-0002-9604-5136
authors.initials: NJ
authors.lastname: Rogers
authors.affiliation: School of Chemistry, University of Southampton , Highfield, Southampton SO17 1BJ, U.K.
authors.forename: Elizaveta A
authors.identifier: http://orcid.org/0000-0003-4407-1882
authors.initials: EA
authors.lastname: Suturina
authors.affiliation: School of Chemistry, University of Southampton , Highfield, Southampton SO17 1BJ, U.K.
authors.forename: Ilya
authors.initials: I
authors.lastname: Kuprov
authors.affiliation: Department of Chemistry, Durham University , South Road, Durham DH1 3LE, U.K.
authors.forename: Juan A
authors.identifier: http://orcid.org/0000-0001-9181-8892
authors.initials: JA
authors.lastname: Aguilar
authors.affiliation: Department of Chemistry, Durham University , South Road, Durham DH1 3LE, U.K.
authors.forename: Andrei S
authors.identifier: http://orcid.org/0000-0002-4912-0981
authors.initials: AS
authors.lastname: Batsanov
authors.affiliation: Department of Chemistry, Durham University , South Road, Durham DH1 3LE, U.K.
authors.forename: Dmitry S
authors.initials: DS
authors.lastname: Yufit
authors.affiliation: Department of Chemistry, Durham University , South Road, Durham DH1 3LE, U.K.
authors.forename: David
authors.identifier: http://orcid.org/0000-0001-5281-5146
authors.initials: D
authors.lastname: Parker