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Title: 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

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)
Authors:
 [1] ;  [2] ;  [1] ;  [2] ;  [3] ;  [4] ;  [5] ;  [1]
  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)
  2. (China)
  3. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China). E-mail: Liming_Wu@fjirsm.ac.cn
  4. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China). E-mail: chenl@fjirsm.ac.cn
  5. Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002 (China)
Publication Date:
OSTI Identifier:
20905385
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal 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)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; COPPER IODIDES; DENSITY FUNCTIONAL METHOD; FLUORESCENCE; INTERACTIONS; LEAD IODIDES; MONOCRYSTALS; ORGANIC PHOSPHORUS COMPOUNDS; SPACE GROUPS; SYNTHESIS; TRICLINIC LATTICES; X-RAY DIFFRACTION