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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Syntheses and crystal structures of two heterometallic iodoplumbates containing mixed-valence copper(I/II)
1Engineering Research Center of Environment-Friendly Functional Materials, Ministry of Education, College of Materials Science and Engineering, Huaqiao University, Xiamen, Fujian 361021, People's Republic of China.
Abstract:
Mixed-valence copper(I/II) atoms have been introduced successfully into a Pb/I skeleton to obtain two heterometallic iodoplumbates, namely poly[bis(tetra-n-butylammonium) [bis(μ3-dimethyldithiocarbamato)dodeca-μ3-iodido-hexa-μ2-iodido-tetracopper(I)copper(II)hexalead(II)]], {(C16H36N)2[Cu4ICuIIPb6(C3H6NS2)2I18]}n, (I), and poly[[μ3-iodido-tri-μ2-iodido-iodido[bis(1,10-phenanthroline)copper(I)]copper(I)copper(II)lead(II)] hemiiodine], {[CuICuIIPbI5(C12H8N2)2]·0.5I2}n, (II), under solution and solvothermal conditions, respectively. Compound (I) contains two-dimensional anionic layers, which are built upon the linkages of CuII(S2CNMe2)2 units and one-dimensional anionic Pb/I/CuI chains. Tetra-n-butylammonium cations are located between the anionic layers and connected to them via C-H...I hydrogen-bonding interactions. Compound (II) exhibits a one-dimensional neutral structure, which is composed of [PbI5] square pyramids, [CuII4] tetrahedra and [CuIIN4I] trigonal bipyramids. Face-to-face aromatic π-π stacking interactions between adjacent 1,10-phenanthroline ligands stabilize the structure and assemble compound (II) into a three-dimensional supramolecular structure. I2 molecules lie in the voids of the structure.
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