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Issue 17, 2013
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Copper(ii) chemistry of the functionalized macrocycle cyclam tetrapropionic acid

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Abstract

The CuII complex of H4TETP (H4TETP = 1,4,8,11-tetraazatetradecane-1,4,8,11-tetrapropionic acid) is five-coordinate with a distorted square-pyramidal structure (τ = 0.45; i.e. the geometry is nearly half-way between square-pyramidal and trigonal-bipyramidal) and a relatively long Cu–N and a short Cu–O bond; the comparison between powder and solution electronic spectroscopy, the frozen solution EPR spectrum and ligand-field-based calculations (angular overlap model, AOM) indicate that the solution and solid state structures are very similar, i.e. the complex has a relatively low “in-plane” and a significant axial ligand field with a dx2y2 ground state. The ligand-enforced structure is therefore shown to lead to a partially quenched Jahn–Teller distortion and to a relatively low complex stability, lower than with the corresponding acetate-derived ligand H4TETA. This is confirmed by potentiometric titration and by the biodistribution with 64Cu-labeled ligands which show that the uptake in the liver is significantly increased with the H4TETP-based system.

Graphical abstract: Copper(ii) chemistry of the functionalized macrocycle cyclam tetrapropionic acid

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Supplementary files

Article information


Submitted
05 Oct 2012
Accepted
26 Nov 2012
First published
27 Nov 2012

Dalton Trans., 2013,42, 6142-6148
Article type
Paper

Copper(II) chemistry of the functionalized macrocycle cyclam tetrapropionic acid

P. Comba, F. Emmerling, M. Jakob, W. Kraus, M. Kubeil, M. Morgen, J. Pietzsch and H. Stephan, Dalton Trans., 2013, 42, 6142
DOI: 10.1039/C2DT32356G

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