SYNTHESIS, CHARACTERIZATION AND COMPLEXATION PROPERTIES OF A HETERODITOPIC CRYPTAND-L TOWARDS CU-II AND ZN-II - CRYSTAL-STRUCTURES OF L-CENTER-DOT-3H(2)O AND [ZNL][CLO4](2)CENTER-DOT-2H(2)O
P. Ghosh et Pk. Bharadwaj, SYNTHESIS, CHARACTERIZATION AND COMPLEXATION PROPERTIES OF A HETERODITOPIC CRYPTAND-L TOWARDS CU-II AND ZN-II - CRYSTAL-STRUCTURES OF L-CENTER-DOT-3H(2)O AND [ZNL][CLO4](2)CENTER-DOT-2H(2)O, Journal of the Chemical Society. Dalton transactions, (15), 1997, pp. 2673-2676
A new heteroditopic cryptand (L) has been synthesized in high yields,
at 5 degrees C and in absence of any templating metal ion, by tripod-t
ripod 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 di
stance of 5.291 Angstrom between the two bridgehead nitrogens. The cry
ptand forms mononuclear cryptates of the general formula [ML][ClO4](2)
with copper(II) and zinc(II) perchlorates. The crystal structure of [
ZnL][ClO4](2) . 2H(2)O was determined. The Zn-II occupies the N-4 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 liga
nd-to-metal charge transfer at 275 nm in acetonitrile solution at 298
K indicative of pseudo-tetrahedral CuN4 co-ordination. However, its EP
R spectral characteristics in the solid state or in solution are typic
al of a magnetically concentrated complex.