초록
Cu(II) hexaazamacrotricyclic complexes $[Cu(L)](ClO_4)_2$ and $[(Cu(L)Cl]ClO_4$, where L = 1,3,6,9,11,14-hexaazatricyclo$[12.2.1.1^{6,9}]octadecane(L_1)$ or 1,3,6,10,12,15-hexaazatricyclo$[13.3.1.1^{6,10}]eicosane(L_2)$, have been prepared by the simple template condensation reactions of triamines, diethylenetriamine for $L_1$, and N-(2-aminoethyl)-1,3-propanediamine for $L_2$, with formaldehyde in the presence of $Cu(OAc)_2\;or\;CuCl_2$. The Cu(II) complexes of $L_1$ contain two 1,3-diazacyclopentane ring moieties and those of $L_2$ contain two 1,3-diazacyclohexane ring moieties that are fused to the 14-membered macrocyclic framework. Spectra indicate that complexes $[Cu(L)](ClO_4)_2\;and\;[Cu(L)Cl]ClO_4$ have square-planar and square-pyramidal chromophores, respectively. square-planar $[Cu(L)](ClO_4)_2$ are remarkably stable against ligand dissociation in acidic aqueous solutions. Square-pyramidal $[Cu(L)Cl]ClO_4$ complexes dissociate their axial Cl-ligands easily in aqueous solutions to form $[Cu(L)H_2O]^{2+}$ species. Infrared and UV/vis absorption spectra of the Cu(II) complexes reveal that Cu-N interactions and the ligand field strengths are significantly weaker in the complexes of $L_2$ than in the complexes of $L_1$.