Issue 12, 2003
From the journal:

Dalton Transactions

Solid-state and solution properties of the lanthanide complexes of a new nonadentate tripodal ligand derived from 1,4,7-triazacyclononane

Christelle Gateau,a   Marinella Mazzanti,*a   Jacques Pécaut,b   Frank A. Dunandc  and  Lothar Helmc  

* Corresponding authors

a Laboratoire de Reconnaissance Ionique, Service de Chimie Inorganique et Biologique (FRE 2600), Département de Recherche Fondamentale sur la Matière Condensée, CEA-Grenoble, Cedex 09, 38054 Grenoble, France
E-mail: mazzanti@drfmc.ceng.cea.fr

b Laboratoire de Coordination et Chiralité, Service de Chimie Inorganique et Biologique (FRE 2600), Département de Recherche Fondamentale sur la Matière Condensée, CEA-Grenoble, Cedex 09, 38054 Grenoble, France

c Institut de Chimie Minérale et Analytique, Université de Lausanne, BCH CH-1015 Lausanne, Switzerland

Abstract

The synthesis of the potentially nonadentate ligand 1,4,7-tris[(6-carboxypyridin-2-yl)methyl]-1,4,7-triazacyclononane (H3tpatcn), a new derivative of 1,4,7-triazacyclononane N-functionalised with three pyridinecarboxylate arms, is described. The complexes of four lanthanide ions (Nd, Eu, Gd, Lu) of this ligand have been prepared and structurally characterised. These complexes, which have high water solubility, show highly rigid C3 symmetric solution structures. All the complexes present mononuclear nine-coordinated solid-state structures. The coordination polyhedron is a slightly distorted tricapped trigonal prism. The NMRD (Nuclear Magnetic Relaxation Dispersion) profiles measured for the [Gd(tpatcn)] complex indicate that the second-sphere contribution arising from the presence of water molecules tightly hydrogen-bonded to the carboxylate moieties on the surface of the complex are not large enough to explain the very high relaxivity of the previously reported [Gd(tpaa)(H2O)2] complex (H3tpaa = α,α′,α″-nitrilotri(6-methyl-2-pyridinecarboxylic acid)). In fact the low-field relaxivity of [Gd(tpatcn)] more likely points to a favorable electronic relaxation rate.

Graphical abstract: Solid-state and solution properties of the lanthanide complexes of a new nonadentate tripodal ligand derived from 1,4,7-triazacyclononane

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Article information

DOI
https://doi.org/10.1039/B303079B
Article type
Paper
Submitted
18 Mar 2003
Accepted
23 Apr 2003
First published
20 May 2003

Dalton Trans., 2003, 2428-2433

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Solid-state and solution properties of the lanthanide complexes of a new nonadentate tripodal ligand derived from 1,4,7-triazacyclononane

C. Gateau, M. Mazzanti, J. Pécaut, F. A. Dunand and L. Helm, Dalton Trans., 2003, 2428 DOI: 10.1039/B303079B

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