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DOI: 10.1039/A701692A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2673-2676

Synthesis, characterization and complexation properties of a heteroditopic cryptand L towards CuII and ZnII: crystal structures of L·3H2O and [ZnL][ClO4]2·2H2O [hair space]

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Pradyut Ghosh and Parimal K. Bharadwaj

Abstract

A new heteroditopic cryptand (L) has been synthesized in high yields, at 5 °C and in absence of any templating metal ion, by tripod–tripod Schiff-base condensation of tris(3-aminopropyl)amine and 2,2′,2″-nitrilotris(ethyleneoxy)tris(benzaldehyde) followed by reduction in situ with NaBH4. The molecule has an endo-endo conformation with a distance of 5.291 Å between the two bridgehead nitrogens. The cryptand forms mononuclear cryptates of the general formula [ML][ClO4]2 with copper(II) and zinc(II) perchlorates. The crystal structure of [ZnL][ClO4]2·2H2O was determined. The ZnII occupies the N4 end of the cavity in an almost ideal tetrahedral geometry. The blue copper(II) cryptate exhibits ligand-field bands at 875 and 745 nm and a ligand-to-metal charge transfer at 275 nm in acetonitrile solution at 298 K indicative of pseudo-tetrahedral CuN4 co-ordination. However, its EPR spectral characteristics in the solid state or in solution are typical of a magnetically concentrated complex.

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