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Article Dans Une Revue Inorganic Chemistry Année : 2014

A Twelve-​Coordinated Iodide in a Cuboctahedral Silver(I) Skeleton

Jian-Hong Liao
  • Fonction : Auteur
Camille Latouche
Bing Li
  • Fonction : Auteur
Samia Kahlal
C. W. Liu
  • Fonction : Auteur

Résumé

Three new halide-centered octanuclear silver(I) complexes, [Ag8(X){S2P(CH2CH2Ph)2}6](PF6), X = F(-), 1; Cl(-), 2; Br(-), 3; were prepared in the presence of the corresponding halide anions with silver(I) salts and dithiophosphinate ligands. Structure analyses displayed that a Ag8 cubic core can be modulated by the size effect of the central halide; however, an iodide-centered Ag8 cluster was not found under similar reaction conditions. Interestingly, a luminescent dodecanuclear silver(I) cluster, [Ag12(μ12-I)(μ3-I)4{S2P(CH2CH2Ph)2}6](I), 4; was then synthesized. The structure of 4 contains a novel μ12-I at the center of a cuboctahedral silver(I) atom cage, which is further stabilized by four additional μ3-I and six dithiophosphinate ligands. To the best of our knowledge, the μ12-I revealed in 4 is the highest coordination number for a halide ion authenticated by both experimental and computational studies. Previously, the μ12-I was only observed in [PyH][{TpMo(μ3-S)4Cu3}4(μ12-I)]. The synthetic details, spectroscopic studies including multinuclear NMR and ESI-MS, structure elucidations by single crystal X-ray diffraction, and photoluminescence of 4 are reported herein.
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Dates et versions

hal-00945260 , version 1 (12-02-2014)

Identifiants

Citer

Jian-Hong Liao, Camille Latouche, Bing Li, Samia Kahlal, Jean-Yves Saillard, et al.. A Twelve-​Coordinated Iodide in a Cuboctahedral Silver(I) Skeleton. Inorganic Chemistry, 2014, 53 (04), pp.2260-2267. ⟨10.1021/ic402960e⟩. ⟨hal-00945260⟩
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