Effect of bridging anions on the structure and stability of phenoxide bridged zinc dipicolylamine coordination complexes

A series of four related phenol derivatives, with 2,2′-dipicolylamine substituents at the ortho positions, were prepared and their Zn 2+ coordination complexes studied by spectroscopic methods. X-ray crystal diffraction analysis of a dinuclear zinc complex with two bridging acetate anions showed a t...

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Bibliographic Details
Published in:Supramolecular chemistry 2013-06, Vol.25 (6), p.315-322
Main Authors: O'Neil, Edward J., Jiang, Hua, Smith, Bradley D.
Format: Article
Language:English
Subjects:
anion recognition
Ligands
NMR
Nuclear magnetic resonance
spectroscopic analysis
titration
X-ray crystallography
Zinc
zinc coordination
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Summary:A series of four related phenol derivatives, with 2,2′-dipicolylamine substituents at the ortho positions, were prepared and their Zn 2+ coordination complexes studied by spectroscopic methods. X-ray crystal diffraction analysis of a dinuclear zinc complex with two bridging acetate anions showed a ternary structure with highly charged interior and lipophilic exterior, which helps explain why this class of water-soluble complexes can effectively diffuse through cell membranes. The stability of the dinuclear zinc complexes in aqueous solution was found to be strongly anion dependent; that is, bridging oxyanions, such as acetate and pyrophosphate, lock the two Zn 2+ cations to the surrounding ligand and greatly enhance ligand/zinc affinity. Overall, the results provide new insight into the structural and mechanistic factors that control the recognition and chemosensing performance of phenoxide bridged dipicolylamine molecular probes.
ISSN:1061-0278
1029-0478
DOI:10.1080/10610278.2013.776170