Hao-Hong Li

Incorporating a Transition Metal Complex into Polymeric Iodoplumbate: Structure Characterization, Properties and Theoretical Study of a Unprecedented Hybrid Semiconductor: {[Cu(en)2][Pb2I6]}n

A hybrid semiconductor {[Cu(en)2][Pb2I6]}n (1) (en = ethylenediamine) templated by a transition metal complex was synthesized and structurally characterized. The title compound consists of discrete structure-directing molecules (transition metal complex) and an inorganic iodoplumbate polymer. The iodoplumbate polymer could be described as a three-dimensional network constructed from a [Pb2I8]n4– double chain bridged by iodine. [Cu(en)2]2+ structure-directing cations are discrete, and interact with the inorganic moiety by strong static attraction and the H-bond of N–H···I to give a so-called hybrid structure. Experimental and theoretical optical property investigations indicate that 1 possesses semiconductor properties. A density functional theory calculation was executed to probe the regulation effect on the introduction of a second metal.

Synthesis, Characterization, and Electronic Structures of Organically Templated Lead Halides with One- and Two-Dimensional Hybrid Structures, [(nbq)(PbI3)]n and {[(CH3)3NC2H4N(CH3)3]3(Pb6I18)}n

Two new organically templated lead(ii) iodide complexes, [(nbq)(PbI3)]n 1 and {[(CH3)3NC2H4N(CH3)3]3(Pb6I18)}n 2, have been synthesized in the presence of aromatic and aliphatic quaternary ammonium compounds, N-(n-butyl)quinolinium (nbq+) and [(CH3)3NC2H4N(CH3)3]2+, respectively, acting as structure-directing agents. Both 1 and 2 consist of uncoordinated structure-directing agents and inorganic moieties bound to the organic structure-directing agents. In 1, an inorganic (PbI3–)n one-dimensional polyanion chain is built up by face-sharing of distorted PbI6 tetrahedra. The inorganic framework of 2 presents a two-dimensional arrangement that could be discussed in terms of [Pb3I10]4– building blocks. Static attractive interactions between organic countercations and inorganic moieties were revealed through the crystal packing. Density functional theory calculations indicate that 1 possesses semiconductor properties, tuned by the π-electrons of nbq+. In contrast, 2 is conductive in the direction of aliphatic quaternary ammonium moiety.