Metallocapped complexation of the thallium(I) ion with calix[4]crown-6 (1) and three different calix[4]biscrown-6 derivatives (2-4) has been investigated by a combination of 203Tl and 1H NMR in a CD3CN/CDCl3 (4:1 v/v) solution. The results clearly revealed the formation in solution of mono- and dithallium(I) complexes in which the metal cations are held in the ligands’ cavities close to the calix[4]arene ring. In addition, a solid state mononuclear complex between 1,3-calix[4]bis-o-benzo-crown-6 (3) and TlClO4 was prepared, and its X-ray crystal structure was determined. The results of the structural data in solution and the solid state suggested that the calix[4]crown-6 derivatives considered provide π cavities as active sites for the complexation of thallium(I) ions.
Cation-π Interaction in Complex Formation Between Tl+ Ion and Calix[4]crown-6 and Some Calix[4]biscrown-6 Derivatives: Thallium-203 NMR, Proton NMR and X-Ray Evidences
LIPPOLIS, VITO;
2010
Abstract
Metallocapped complexation of the thallium(I) ion with calix[4]crown-6 (1) and three different calix[4]biscrown-6 derivatives (2-4) has been investigated by a combination of 203Tl and 1H NMR in a CD3CN/CDCl3 (4:1 v/v) solution. The results clearly revealed the formation in solution of mono- and dithallium(I) complexes in which the metal cations are held in the ligands’ cavities close to the calix[4]arene ring. In addition, a solid state mononuclear complex between 1,3-calix[4]bis-o-benzo-crown-6 (3) and TlClO4 was prepared, and its X-ray crystal structure was determined. The results of the structural data in solution and the solid state suggested that the calix[4]crown-6 derivatives considered provide π cavities as active sites for the complexation of thallium(I) ions.
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