Three pillared-layer 3d-4f heterometallic frameworks based on tetranuclear lanthanide clusters

Three 3D heterometallic 3d-4f MOFs, formulated as [Gd4L12(Cu10I8)(H2O)(10)]center dot 2ClO(4)center dot 4H(2)O (1), [La-4(Ox)(2)L-8(Cu7I5)(H2O)(4)]center dot 2ClO4 center dot 4H(2)O (2), and [La4Na(Ox)(3)L-8(Cu7I6)(H2O)3]center dot 5H(2)O(3) [where Ox = oxalate, HL = 4-pyridin-4-ylbenzonic acid], have been made under hydrothermal conditions. All the MOFs are characterized by elemental analysis, IR, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. These novel 3D pillared-layer frameworks are constructed from 2D lanthanide-organic layers based on tetranuclear lanthanide clusters, and pillared by diverse copper(I) halide motifs. The oxalate is introduced as a coligand to make the hook-like tetramer in compound 1 into compact butterfly-like tetramer in compounds 2 and 3 due to its size preference.