A bridge to coordination isomer selection in lanthanide(III) DOTA-tetraamide complexes

Jeff Vipond, Mark Woods, Piyu Zhao, Gyula Tircsó, Jimin Ren, Simon G. Bott, Doug Ogrin, Garry E. Kiefer, Zoltan Kovacs, A. Dean Sherry

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Interest in macrocyclic lanthanide complexes such as DOTA is driven largely through interest in their use as contrast agents for MRI. The lanthanide tetraamide derivatives of DOTA have shown considerable promise as PARACEST agents, taking advantage of the slow water exchange kinetics of this class of complex. We postulated that water exchange in these tetraamide complexes could be slowed even further by introducing a group to sterically encumber the space above the water coordination site, thereby hindering the departure and approach of water molecules to the complex. The ligand 8O2-bridged DOTAM was synthesized in a 34% yield from cyclen. It was found that the lanthanide complexes of this ligand did not possess a water molecule in the inner coordination sphere of the bound lanthanide. The crystal structure of the ytterbium complex revealed that distortions to the coordination sphere were induced by the steric constraints imposed on the complex by the bridging unit. The extent of the distortion was found to increase with increasing ionic radius of the lanthanide ion, eventually resulting in a complete loss of symmetry in the complex. Because this ligand system is bicyclic, the conformation of each ring in the system is constrained by that of the other; in consequence, inclusion of the bridging unit in the complexes means only a twisted square, antiprismatic coordination geometry is observed for lanthanide complexes of 8O2-bridged DOTAM.

Original languageEnglish (US)
Pages (from-to)2584-2595
Number of pages12
JournalInorganic Chemistry
Volume46
Issue number7
DOIs
StatePublished - Apr 2 2007

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Lanthanoid Series Elements
Isomers
isomers
Water
water
ligands
Ligands
Ytterbium
ytterbium
Molecules
molecules
Magnetic resonance imaging
Contrast Media
Conformations
inclusions
Crystal structure
crystal structure
radii
Ions
rings

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

A bridge to coordination isomer selection in lanthanide(III) DOTA-tetraamide complexes. / Vipond, Jeff; Woods, Mark; Zhao, Piyu; Tircsó, Gyula; Ren, Jimin; Bott, Simon G.; Ogrin, Doug; Kiefer, Garry E.; Kovacs, Zoltan; Sherry, A. Dean.

In: Inorganic Chemistry, Vol. 46, No. 7, 02.04.2007, p. 2584-2595.

Research output: Contribution to journalArticle

Vipond, J, Woods, M, Zhao, P, Tircsó, G, Ren, J, Bott, SG, Ogrin, D, Kiefer, GE, Kovacs, Z & Sherry, AD 2007, 'A bridge to coordination isomer selection in lanthanide(III) DOTA-tetraamide complexes', Inorganic Chemistry, vol. 46, no. 7, pp. 2584-2595. https://doi.org/10.1021/ic062184+
Vipond, Jeff ; Woods, Mark ; Zhao, Piyu ; Tircsó, Gyula ; Ren, Jimin ; Bott, Simon G. ; Ogrin, Doug ; Kiefer, Garry E. ; Kovacs, Zoltan ; Sherry, A. Dean. / A bridge to coordination isomer selection in lanthanide(III) DOTA-tetraamide complexes. In: Inorganic Chemistry. 2007 ; Vol. 46, No. 7. pp. 2584-2595.
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