A reversible polymorphic phase change which affects the luminescence and aurophilic interactions in the gold(I) cluster complex, [μ3-S(AuCNC7H13)3](SbF6)

被引：71

作者：

Gussenhoven, EM ^{[1
]}

Fettinger, JC ^{[1
]}

Pham, DM ^{[1
]}

Malwitz, MM ^{[1
]}

Balch, AL ^{[1
]}

机构：

[1] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 31期

关键词：

D O I：

10.1021/ja052799q

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Crystallographic examination of [μ3-S(AuCNC7H13)3](SbF6) shows that it undergoes a reversible phase change from orthorhombic to monoclinic upon cooling. At 190 K, the structure shows that two cations self-associate to form a pseudo-octahedral array of six gold atoms connected by both intra- and interionic aurophilic interactions. On cooling, the clusters become less symmetric, and in one, the interionic Au⋯Au separations increase, while they decrease in the second cluster. The luminescence of crystalline [μ3-S(AuCNC7H13)3](SbF6) shows corresponding changes in emission, with two emissions of similar lifetimes but with different excitations at 77 K, but only a single emission at 298 K. In contrast, [μ3-S(AuCNC6H11)3](PF6), which has a similar structure to that of the high-temperature form of [μ3-S(AuCNC7H13)3](SbF6), does not undergo a phase change or change in its luminescence upon cooling. Copyright © 2005 American Chemical Society.

引用

页码：10838 / 10839

页数：2

共 19 条

[1] Synthesis and structural characterization of [NEt4][Fe3(μ3-O)(μ3-AUPPh3)(μ-CO)3(CO)6], the new [Au6(μ3-S)2(PPh3)6][Fe3(μ3-S)(μ-AuPPh3)(CO)9]2 and [Au6(μ-S)2(PPh3)6][Fe5(μ3-S)2(CO)14] ionic solids containing assemblages of cluster-cations and cluster-anions [J].