TY - JOUR
T1 - Selenium-centered, undecanuclear silver cages surrounded by iodo and dialkyldiselenophosphato ligands. Syntheses, structures, and photophysical properties
AU - Liu, C. W.
AU - Shang, Iu Jie
AU - Fu, Rei Jen
AU - Liaw, Ben Jie
AU - Wang, Ju Chun
AU - Chang, I. Jy
PY - 2006/3/6
Y1 - 2006/3/6
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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U2 - 10.1021/ic052015+
DO - 10.1021/ic052015+
M3 - Article
C2 - 16499400
AN - SCOPUS:33645047683
VL - 45
SP - 2335
EP - 2340
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 5
ER -