Polyamine-based anion receptors:: Extraction and structural studies

In the discussion that follows some of the more recent progress in the area of anion binding by synthetic polyamine receptors is presented, with emphasis given to work undertaken by the authors' groups. A continuing theme in these studies has been the relationship between receptor structure and its anion extraction properties. Systematic solvent extraction and structural studies for halide and perrhenate complexes with polyamines of tripodal, macrocyclic and macrobicyclic architecture that contain both aromatic moieties and four to eight amine functions have been performed in order to derive relevant structure-binding/extractability relationships. The results demonstrate that the binding and extraction behaviour of the polyamines towards halides and perrhenate is a complex function of their structural features, degree of protonation and lipophilic properties. The extraction is characterized by the preferred formation of mono- and diprotonated amine species in the organic phase. X-ray structure studies of iodide and perrhenate complexes with open-chain tetraamino derivatives and octaamino cryptands in different protonation states lead to the conclusion that in the first case only limited chelation of the anion occurs and in the second only highly protonated species are able to encapsulate the anion. The structural patterns observed are strongly influenced by the presence of water molecules in the crystals. (c) 2006 Elsevier B.V. All rights reserved.