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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Abstract

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
Volume45
Issue number5
DOIs
Publication statusPublished - 2006 Mar 6

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Iodides
Selenium
selenium
Silver
iodides
silver
Ligands
Atoms
ligands
synthesis
Prisms
Luminescence
mass spectra
prisms
Anions
atoms
bombardment
solid solutions
X-Rays
Single crystals

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Selenium-centered, undecanuclear silver cages surrounded by iodo and dialkyldiselenophosphato ligands. Syntheses, structures, and photophysical properties. / Liu, C. W.; Shang, Iu Jie; Fu, Rei Jen; Liaw, Ben Jie; Wang, Ju Chun; Chang, I-Jy.

In: Inorganic Chemistry, Vol. 45, No. 5, 06.03.2006, p. 2335-2340.

Research output: Contribution to journalArticle

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title = "Selenium-centered, undecanuclear silver cages surrounded by iodo and dialkyldiselenophosphato ligands. Syntheses, structures, and photophysical properties",
abstract = "Three clusters [Ag11(μ9-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 11(μ9-Se)(μ3-I)2{Se 2P(OR)2}6]+, and a diselenophosphate ligand, [Ag11(μ9-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 (μ2,μ2) 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.",
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AU - Liu, C. W.

AU - Shang, Iu Jie

AU - Fu, Rei Jen

AU - Liaw, Ben Jie

AU - Wang, Ju Chun

AU - Chang, I-Jy

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N2 - Three clusters [Ag11(μ9-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 11(μ9-Se)(μ3-I)2{Se 2P(OR)2}6]+, and a diselenophosphate ligand, [Ag11(μ9-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 (μ2,μ2) 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.

AB - Three clusters [Ag11(μ9-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 11(μ9-Se)(μ3-I)2{Se 2P(OR)2}6]+, and a diselenophosphate ligand, [Ag11(μ9-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 (μ2,μ2) 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.

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