Preparation and characterization of a novel hybrid magnetic semiconductor containing rare, one-dimensional mixed-iodide/chloride anion of lead(II)

A new hybrid inorganic–organic magnetic semiconductor [Ni(bipy)3Pb2I4.84Cl1.16·DMF]n (bipy=2,2′-bipyridine) containing novel one-dimensional mixed-halide anion of lead(II) was synthesized by reactions of PbI2, NaI, NiCl2 and bipy in DMF solution, and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the space group C2/c with a=29.260(8) Å, b=15.602(4) Å, c=23.695(6) Å, β=126.815(°), Z=8, V=8660(4) Å3 and consists of a magnetic cation [Ni(bipy)3]2+ in addition to one-dimensional mixed-halide anion, which is built up of face-sharing [PbX6] octahedra. Of the seven crystallographically independent halide sites in this anion, one and five are occupied by Cl and I, respectively, the remaining one has mixed-iodide and -chloride occupancy. The title yellow compound has an optical bandgap of 2.59 eV, and the variable-temperature magnetic susceptibility measurement indicates paramagnetic behavior.

Graphical abstractBased upon magnetic metal-organic complex as template, a novel one-dimensional haloplumbate containing mixed-halide anion has been successfully synthesized. Its structural characteristics, optical bandgap, magnetic and thermal properties are reported.Figure optionsDownload full-size imageDownload as PowerPoint slide