63356-93-4Relevant academic research and scientific papers
Structures and luminescent properties of polynuclear gold(I) halides containing bridging phosphine ligands
Xiao, Hong,Weng, Yu-Xiang,Wong, Wing-Tak,Mak, Thomas C. W.,Che, Chi-Ming
, p. 221 - 226 (1997)
The complexes [AuI(PPh3)] 1, [Au2(μ-dppm)Cl2] 2 [dppm = bis(diphenylphosphine)methane], [Au2(μ-dppm)I2] 3, [Au3(μ-tppm)Cl3] 4 [tppm = tris(diphenylphosphino)methane], [Au3(μ-dpmp)I3] 5, [Au3(μ-dpmp)2Cl2]Cl 6 [dpmp = bis(diphenylphosphinomethyl)phenylphosphine] and [Au3(μ-dpmp)2I2]I 7 were prepared. The crystal structures of 5-7 have been established by X-ray crystal analysis. The measured intramolecular Au-Au distances are 3.136(1) A in 5, 2.946(3) and 2.963(3) A in 6 and 2.952(1) and 3.020(1) A in 7. Extended-Hueckel molecular orbital calculations revealed that the 6p orbitals of iodide and 5d orbitals of gold(I) make a significant contribution to the highest occupied molecular orbitals of 5 and of 2 and 4 respectively. The lowest unoccupied molecular orbitals of these complexes mainly comprise π* orbitals of the phosphines. The photophysical properties of 1-6 have been studied. All show dual emissions. The low-energy emissions at around 660-680 nm have a small red shift in energy from chloro to iodo complexes, and a much higher intensity at room temperature than at 77 K. These are attributed to triplet states with mixed 3m.m.l.c.t. (metal-metal to ligand charge transfer, gold→phosphine) and 3l.l.c.t. (ligand to ligand charge transfer, halide to phosphine) characters. The high-energy emissions at around 460-530 nm are more prominent at 77 K and assigned to intraligand and or 3m.l.c.t. (metal to ligand charge transfer) transitions. The temperature effects on the luminescence lifetimes of these complexes have also been studied.
Governing the oxidative addition of iodine to gold(I) complexes by ligand tuning
Schneider, Daniel,Schier, Annette,Schmidbaur, Hubert
, p. 1995 - 2005 (2007/10/03)
The impact of addition of iodine to gold compounds which is strongly ligand-dependent and indicate a threshold in the oxidation potentials was investigated. A large series of tertiary phosphines were used as ligands for the oxidative addition of iodine. The reactions were followed by 31P NMR spectroscopy and the products crystallized from dichromethane-pentane solutions. Complexes with small triakylphosphines were readily oxidized, while those with more bulky ligands were not. No oxidation took place when the ligands were taken from the triaryphosphine series.
