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Dalton Trans. 2006 Dec 7;(45):5423-8. Epub 2006 Sep 29.

Synthesis and characterisation of dimeric eight-coordinate lanthanide(III) complexes of a macrocyclic tribenzylphosphinate ligand.

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1
Department of Chemistry, Durham University, South Road, Durham, UK DH1 3LE.

Abstract

The macrocyclic ligand 1,4,7,10-tetraazacyclododecane-1,4,7-triyl(methylenebenzyl-phosphinic acid) H3L3, has been prepared and its complexes with Eu, Gd and Tb(III) studied by NMR, relaxometry, luminescence and single crystal X-ray crystallography. In solution and in the crystal, the complexes have eight-coordinate metal centres with bridging phosphinate groups linking the two twisted square antiprismatic coordination polyhedra. A single stereoisomer crystallises from solution with an RRR and SSS configuration at the P centres in each sub-unit. The relaxivity of [GdL3]2 is low (1.9 mM-1 s-1, 298 K, 20 MHz), consistent with the absence of any proximate water molecules. The terbium dimer possesses a relatively long excited state lifetime (2.47 ms, 298 K).

PMID:
17102868
DOI:
10.1039/b612189f

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