PbI{sub 4}Cu{sub 2}(PPh{sub 3}){sub 4}: A heterometallic iodide with unusual cis-divacant octahedral coordination sphere for lead: Synthesis, structure, red-infrared fluorescence and theoretical studies
- State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)
- Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002 (China)
A new heterometallic iodide, PbI{sub 4}Cu{sub 2}(PPh{sub 3}){sub 4}, was synthesized by reactions of PbI{sub 2}, CuI and triphenylphosphine (PPh{sub 3}) in DMF solution. The single-crystal X-ray diffraction analyses show that Pb(II) center adopts an unusual cis-divacant octahedral geometry. Crystal data: triclinic, space group P1-bar , a=12.3455(2)A, b=13.8673(1)A, c=21.3421(1)A, {alpha}=106.623(4){sup o}, {beta}=103.478(6){sup o}, {gamma}=93.574(5){sup o}, V=3371.83(6)A{sup 3} and Z=2. Density function theory (DFT) calculations and fragment orbital interaction analyses reveal the presence of a three-center four-electron (3c-4e) hypervalent bonding about lead; and the formation of the unusual cis-divacant [PbI{sub 4}]{sup 2-} octahedron is energetically favorable. The title yellow compound has an optical bandgap of 2.69eV and shows remarkable red-infrared fluorescence emission at 732nm with lifetime of 24{mu}s which is assigned as an iodine 5p-lead 6s to PPh{sub 3}-lead 6p charge transfer (XM-LM-CT)
- OSTI ID:
- 20905385
- Journal Information:
- Journal of Solid State Chemistry, Vol. 179, Issue 8; Other Information: DOI: 10.1016/j.jssc.2006.04.019; PII: S0022-4596(06)00237-4; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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