Selenium-centered, undecanuclear silver cages surrounded by iodo and dialkyldiselenophosphato ligands. Syntheses, structures, and photophysical properties

C. W. Liu, Iu Jie Shang, Rei Jen Fu, Ben Jie Liaw, Ju Chun Wang, I. Jy Chang

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Three clusters [Ag119-Se)(μ3-I) 3{Se2P(OR)2}6] (R = Et, 1; iPr, 2; 2Bu, 3) were isolated from the reaction of [Ag(CH3CN)4](PF6), NH4[Se 2P(OR)2], and Bu4NI in a molar ratio of 4:3:1 in CH2Cl2 in 47-55% yield. Compounds 1 and 2 can also be synthesized with high yield from the reaction of Ag10(Se)[Se 2P(OR)2]8 with 8 equiv of Bu4NI. In the positive fast atom bombardment mass spectra of 1-3, two major peaks that correspond to the intact molecule with the loss of an iodide ion, [Ag 119-Se)(μ3-I)2{Se 2P(OR)2}6]+, and a diselenophosphate ligand, [Ag119-Se)-(μ3-I) 3{Se2P(OR)2}5]+, were identified. Single-crystal X-ray analyses of 2 and 3 reveal an Ag11Se core stabilized by three iodide anions and six diselenophosphato ligands in a tetrametallic tetraconnective (μ22) coordination mode. The central core adopts the geometry of a 3,3,4,4,4-pentacapped trigonal prism with a selenium atom in the center. In addition, weak intermolecular Se⋯I interactions exist in 2 and form a one-dimensional polymeric chain structure. Furthermore, all compounds exhibit orange-red luminescence in both the solid state and solution.

Original languageEnglish
Pages (from-to)2335-2340
Number of pages6
JournalInorganic Chemistry
Issue number5
Publication statusPublished - 2006 Mar 6


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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