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A structural study of the synergic envelopment of acetonitrile by a Cd(II) activated molecular receptor formed from cyclen with appended 2-hydroxy-3-phenylpropyl moieties
Authors:Timothy S Robinson  Stephen F Lincoln  Edward RT Tiekink
Institution:a School of Chemistry, Physics and Earth Sciences, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia
b Department of Chemistry, The University of Adelaide, Adelaide, SA 5005, Australia
Abstract:The newly synthesised metal ion activated molecular receptor Cd{1,4,7,10-tetrakis((R)-(−)-2-hydroxy-3-phenylpropyl)-1,4,7,10-tetraazacyclododecane}](ClO4)2 (hereafter CdL](ClO4)2) acts as a molecular receptor for acetonitrile. The receptor was characterised by X-ray crystallography in its metal free form, as its Cd(II) complex with no included molecule, as its Cd(II) complex with an included acetonitrile molecule and, for comparative purposes, as its Zn(II) complex with a partially included acetonitrile molecule. These structural studies demonstrated that the Cd(II) complex is eight-coordinate, with the potential to form a well defined hydrophobic cavity that can contain one acetonitrile molecule through four hydrogen-bonds, whereas the Zn(II) complex is six-coordinate, with a less rigidly constituted binding cavity, such that when solvated by acetonitrile the solvating molecule is retained by only a single hydrogen-bond.
Keywords:Molecular receptor  Crystal structure  Variable temperature NMR  Macrocyclic ligand  Cd(II) complexes
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