Graduate School of Materials and Science, Nara Institute of Science and Technology, NAIST, 8916-5 Takayama, Ikoma, Nara 630-0192, Japan.
Inorg Chem. 2010 Aug 2;49(15):7129-34. doi: 10.1021/ic100948m.
A series of cationic carbene complexes of Au(I) with different types of counteranions, Au{C(OMe)NHMe}(2)(X(-)) (X(-) = CF(3)SO(3)(-), PF(6)(-), CF(3)CO(2)(-), ClO(4)(-), and I(-)), was synthesized, and their intense photoluminescence was studied. These complexes crystallize in the same space group, and the X-ray crystallographic data of these samples revealed the short Au(I)-Au(I) aurophilic distances (3.263-3.335 A), where planar carbene Au(I) complexes are organized into linear stacks. The aurophilic Au(I)-Au(I) interactions found in the crystalline state give rise to phosphorescence with relatively high emission quantum efficiencies, whereas Au{C(OMe)NHMe}(2)(X(-)) complexes show no appreciable emission in solutions. The Au(I)-Au(I) distances in the crystal of Au{C(OMe)NHMe}(2)(X(-)) vary depending on the type of counteranions because the carbene ligands of Au(I) cations are linked through hydrogen bonds with adjacent counteranions. The effects of counteranions on the Au(I)-Au(I) aurophilic interactions allow one to modulate the intense photoluminescence color from blue to yellow by adjusting the counteranions of Au{C(OMe)NHMe}(2)(X(-)) complexes.
一系列具有不同类型抗衡阴离子的金(I)的阳离子卡宾配合物,Au{C(OMe)NHMe}(2)(X(-))(X(-)=CF(3)SO(3)(-), PF(6)(-), CF(3)CO(2)(-), ClO(4)(-), 和 I(-)),被合成,并研究了它们强烈的光致发光。这些配合物在相同的空间群中结晶,这些样品的 X 射线晶体学数据揭示了短的金(I)-金(I)金键距离(3.263-3.335Å),其中平面卡宾金(I)配合物被组织成线性堆叠。在晶态中发现的金键金(I)-金(I)相互作用导致磷光发射具有相对较高的发射量子效率,而Au{C(OMe)NHMe}(2)(X(-))配合物在溶液中没有明显的发射。Au{C(OMe)NHMe}(2)(X(-))晶体中金(I)-金(I)距离因金(I)阳离子的卡宾配体通过氢键与相邻的抗衡阴离子相连而取决于抗衡阴离子的类型而变化。抗衡阴离子对金键金(I)-金(I)相互作用的影响允许通过调节Au{C(OMe)NHMe}(2)(X(-))配合物的抗衡阴离子来调制从蓝色到黄色的强烈光致发光颜色。