A twelve-coordinated iodide in a cuboctahedral silver(I) skeleton.
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.
Department of Chemistry, National Dong Hwa University , Hualien, Taiwan 97401, R. O. C .
Jian-Hong
JH
Liao
Camille
C
Latouche
Bing
B
Li
Samia
S
Kahlal
Jean-Yves
JY
Saillard
C W
CW
Liu
D003198:Computer Simulation; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007454:Iodides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D012834:Silver / Q000737:chemistry*
D056831:Coordination Complexes; D007454:Iodides; D012834:Silver