Nano-Sized Channels Resulting from the Packing of Discrete 3d-4f Metal Complexes in Crystals

The crystal packing of the heterobinuclear complexes [MIIDyIII(valpn)(hfac)2(pb)]center dot 0.67H2O center dot(solvent) generates large and small chan-nels (M = Zn 1a and Cu 2; hfac- = hexafluoroacetylacetonate; valpn2- is the dianion of the Schiff base that resulted from the condensation reaction between o -vanillin and 1,3-diaminopropane; and pb- = 1-pyrenebutyrate). The large channels are padded by CF3 groups arising from the hfac- ligands. The diameter of the almost circular cross-section of the large channels is about 1.2 nm, considering the van der Waals surface. The crystals 1b, resulted from removing the solvent molecules from 1a, were found to host iodine molecules into the small channels: 0.33I2/[ZnDy] 1c. In compounds 1a, 1b, 1c, and 2, the 3d metal ions (ZnII and CuII) show a square-pyramidal geometry. If the 3d metal ion is nickel(II), with an octahedral geometry, the packing of the molecules, [NiIITbIII(MeOH)(valpn)-(hfac)2(pb)]center dot 3, is different, without formation of channels. In all these compounds, the segregation of the trifluoromethyl groups was observed.