Synthesis, fluorescence properties and structural characterization of two heteronuclear Zn(II)-Pr(III) clusters with a chain-shaped ether Schiff base ligand

Two new Zn(II)-Pr(III) heteronuclear clusters were synthesized by interfacial diffusion, [ZnPr(L)(NO3)2(OAc)(CH3OH)]·CH3CN (1) and [Zn4Pr2L4(terephthalate)2]·(NO3)2 (2) (H2L = bis(3-methoxysalicylaldehyde-3-oxopene-1,5-diamine). They have been characterized by elemental analysis, UV-Vis and IR spectroscopy, and single-crystal X-ray diffraction. Structural analysis revealed that 1 has a heterodinuclear structure, with Zn(II) in the inner cavity generated by deprotonated ligands L2- and Pr(III) in the larger outer cavity. Cluster 2 is a heterohexanuclear structure, in which the Pr(III) bridges two [ZnL] to form a heterotrinuclear secondary unit [Zn2PrL2], and then two terephthalates connect two secondary units to form a heterohexanuclear cluster structure. The solid-state fluorescence properties of clusters and ligand show that there are not only slightly blue-shifted fluorescence peak of ligand, but also characteristic fluorescence peaks of Pr(III) ions in the two clusters: 615 nm (3P0→3H6) for 1, 609 nm (1D2→3H4) and 646 nm (3P0→3F2) for 2, respectively. In the two clusters, the difference of ion fluorescence peaks is attributed to the symmetry difference of coordination geometric environment of Pr(III).