Rios Daniel, Pham David M, Fettinger James C, Olmstead Marilyn M, Balch Alan L
Department of Chemistry, University of California, Davis, CA 95616, USA.
Inorg Chem. 2008 Apr 21;47(8):3442-51. doi: 10.1021/ic702481v. Epub 2008 Mar 18.
Depending upon the crystallization conditions, [Au{C(NHMe) 2} 2](AsF 6) forms colorless crystals that display a blue or green luminescence. The difference involves the type of solvate molecule that is incorporated into the crystal and the structure of the chains of cations that are formed upon crystallization. The crystallographically determined structures of blue-glowing [Au{C(NHMe) 2} 2](AsF 6).0.5(benzene), blue-glowing [Au{C(NHMe) 2} 2](AsF 6).0.5(acetone), green-glowing [Au{C(NHMe) 2} 2](AsF 6).0.5(chlorobenzene), and blue-glowing, solvate-free [Au{C(NHMe) 2} 2](EF 6), E = P, As, Sb are reported. All pack with the cations forming extended columns, which may be linear or bent, but all show significant aurophilic interactions. The blue-glowing crystals have ordered stacks of cations with some variation in structural arrangement whereas the green-glowing crystals have disorder in their stacking pattern. Although there is extensive hydrogen bonding between the cations and anions in all structures, in the solvated crystals, the solvate molecules occupy channels but make no hydrogen-bonded contacts. The emission spectra of these new salts taken at 298 and 77 K are reported.
根据结晶条件,Au{C(NHMe)₂}₂形成无色晶体,呈现蓝色或绿色发光。差异涉及纳入晶体的溶剂化分子类型以及结晶时形成的阳离子链的结构。报道了蓝色发光的Au{C(NHMe)₂}₂·0.5(苯)、蓝色发光的Au{C(NHMe)₂}₂·0.5(丙酮)、绿色发光的Au{C(NHMe)₂}₂·0.5(氯苯)以及蓝色发光的无溶剂Au{C(NHMe)₂}₂(E = P、As、Sb)的晶体学测定结构。所有晶体中阳离子形成延伸的柱体,可能是线性或弯曲的,但都显示出显著的亲金相互作用。蓝色发光晶体中阳离子有有序堆叠,结构排列存在一些变化,而绿色发光晶体的堆叠模式无序。尽管在所有结构中阳离子和阴离子之间都存在广泛的氢键,但在溶剂化晶体中,溶剂化分子占据通道但不形成氢键接触。报道了这些新盐在298 K和77 K下的发射光谱。