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Solution Structure of Ln(III) Complexes with Macrocyclic Ligands Through Theoretical Evaluation of 1H NMR Contact Shifts

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† Departamento de Química Fundamental, Facultade de Ciencias, Universidade da Coruña, Campus da Zapateira-Rúa da Fraga 10, 15008 A Coruña, Spain.
‡ Dipartimento di Scienze e Innovazione Tecnologica, Università del Piemonte Orientale “Amedeo Avogadro”, Viale T. Michel 11, 15121 Alessandria, Italy
§ Université de Bretagne Occidentale, UMR-CNRS 6521, UFR des Sciences et Techniques, 6 avenue Victor le Gorgeu, C.S. 93837, 29238 BREST Cedex 3, France
*E-mail: [email protected]
Cite this: Inorg. Chem. 2012, 51, 24, 13419–13429
Publication Date (Web):December 6, 2012
https://doi.org/10.1021/ic302322r
Copyright © 2012 American Chemical Society
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    Abstract

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    Herein, we present a new approach that combines DFT calculations and the analysis of TbIII-induced 1H NMR shifts to quantitatively and accurately account for the contact contribution to the paramagnetic shift in LnIII complexes. Geometry optimizations of different GdIII complexes with macrocyclic ligands were carried out using the hybrid meta-GGA TPSSh functional and a 46 + 4f7 effective core potential (ECP) for Gd. The complexes investigated include [Ln(Me-DODPA)]+ (H2Me-DODPA = 6,6′-((4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylene))dipicolinic acid, [Ln(DOTA)(H2O)]− (H4DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate), [Ln(DOTAM)(H2O)]3+ (DOTAM = 1,4,7,10- tetrakis[(carbamoyl)methyl]-1,4,7,10-tetraazacyclododecane), and related systems containing pyridyl units (Ln = Gd, Tb). Subsequent all-electron relativistic calculations based on the DKH2 approximation, or small-core ECP calculations, were used to compute the 1H hyperfine coupling constants (HFCCs) at the ligand nuclei (Aiso values). The calculated Aiso values provided direct access to contact contributions to the 1H NMR shifts of the corresponding TbIII complexes under the assumption that Gd and Tb complexes with a given ligand present similar HFCCs. These contact shifts were used to obtain the pseudocontact shifts, which encode structural information as they depend on the position of the nucleus with respect to the lanthanide ion. An excellent agreement was observed between the experimental and calculated pseudocontact shifts using the DFT-optimized geometries as structural models of the complexes in solution, which demonstrates that the computational approach used provides (i) good structural models for the complexes, (ii) accurate HFCCs at the ligand nuclei. The methodology presented in this work can be classified in the context of model-dependent methods, as it relies on the use of a specific molecular structure obtained from DFT calculations. Our results show that spin polarization effects dominate the 1H Aiso values. The X-ray crystal structures of [Ln(Me-DODPA)](PF6)·2H2O (Ln = Eu or Lu) are also reported.

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    Absolute deviations (Δδ) of experimental and calculated TbIII-induced 1H NMR shifts in [Tb(Py2N4Py4)]3+ and [Tb(DOTAM)(H2O)]3+ complexes, and optimized cartesian coordinates (Å) of the complexes investigated in this work. This material is available free of charge via the Internet at http://pubs.acs.org.

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