Three-Dimensional Pillared-Layer 3d-4f Heterometallic Coordination Polymers With or Without Halides

Hydrothermal reactions of isonicotinic acid (Hina) and hemimellitic acid (H(3)hma) with lanthanide oxides and copper halides yielded 10 three-dimensional (3D) pillared-layer 3d-4f heterometallic coordination polymers (HCPs) with three structural types. They are formulated as [Ln(2)Cu(2)(mu(2)-X)(hma)(ina)(4)(H2O)(2)](n)center dot 2nH(2)O [Ln = La, X = Cl (I-A), Ln = La, X = Br (I-B), Ln = La, X = I (I-C), Ln = Nd, X = Cl (I-D), Ln = Nd, X = Br (I-E)], [Ln(3)Cu(4.5)I(3.5)(mu(3)-OH)(hma)(ina)(6)(H2O)]center dot nH(2)O [Ln = Pr (II-A), Nd(II-B)], and [LnCu(0.5)(hma)(ina)(H2O)](n)center dot nH(2)O [Ln = La (III-A), Ce (III-B), Pr (III-C)]. All the HCPs are characterized by single-crystal X-ray diffractions. In type I structures, Ln-organic layers are pillared by halide-bridged dinuclear [Cu-2(mu(2)-Cl)(ina)(4)] units through Ln-O bonds. In type II structures, Ln-organic layers are pillared by two different kinds of monovalent Cu-based building units, namely, halide-free [Cu(ina)(2)] and halide-containing [Cu-8(mu(3)-I)(6)(mu(4)-I)(ina)(10)](n). In type III structures, undulate heterometallic Cu(II)-Ln(III) layers are pillared by organic Ma ligands via Ln-O and Cu-N bonds. The solid-state photoluminescent properties of I-D and II-B were also investigated at room temperature.