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Nuclear magnetic resonance, luminescence and structural studies of lanthanide complexes with octadentate macrocyclic ligands bearing benzylphosphinate groups

Journal of the Chemical Society - Dalton Transactions, ISSN: 0300-9246, Issue: 19, Page: 3623-3636
1997
  • 110
    Citations
  • 0
    Usage
  • 28
    Captures
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Metrics Details

  • Citations
    110
    • Citation Indexes
      110
  • Captures
    28

Article Description

The solution and solid-state structures of lanthanide complexes of 1,4,7,10-tetraazacyclododecane-1,4,7,10- tetryltetramethylenetetra(benzylphosphinate), L, and of its o-, m- and p-methoxybenzyl analogues (L, L, L) have been investigated by NMR, relaxometry, crystallographic and photophysical methods. It has been shown that the number of proximate water molecules is dependent on the size of the bound lanthanide ion: the complex [LaL] is nine-co-ordinate and adopts a twisted square-antiprismatic structure with one bound water molecule. The analogous [YL], [YbL], [GdL] and [EuL] complexes also adopt a twisted square-antiprismatic geometry, but are eight-co-ordinate, with no metal-bound water. Relaxivity studies with the gadolinium complexes showed that they are purely 'outer-sphere' contrast agents, but they associate strongly with proteins leading to a pronounced relaxivity enhancement. Detailed biodistribution studies with [GdL] revealed avid biliary uptake at low doses and a well defined tendency for the complex to be cleared more slowly from tumour tissue, allowing tissue differentiation.

Bibliographic Details

Silvio Aime; Andrei S. Batsanov; Mauro Botta; Rachel S. Dickins; Stephen Faulkner; Clive E. Foster; Alice Harrison; Judith A. K. Howard; Janet M. Moloney; Timothy J. Norman; David Parker; Louise Royle; J. A. Gareth Williams

Royal Society of Chemistry (RSC)

Chemistry

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