Cu[Au(CN)2]2(DMSO)2: Golden Polymorphs That Exhibit Vapochromic Behavior
详细信息 查看全文
- 作者：Julie Lefebvre ; Raymond J. Batchelor ; and Daniel B. Leznoff
- 刊名：Journal of the American Chemical Society
- 出版年：2004
- 出版时间：December 15, 2004
- 年：2004
- 卷：126
- 期：49
- 页码：16117 - 16125
- 全文大小：577K
- 年卷期：v.126,no.49(December 15, 2004)
- ISSN：1520-5126
文摘
Two polymorphs of an [Au(CN)2]-based coordination polymer, Cu[Au(CN)2]2(DMSO)2, one green(1) and one blue (2), have been identified. In polymorph 1, alternation of five-coordinate CuII and [Au(CN)2]-units generates 1-D chains, while 2-D corrugated sheets are obtained in polymorph 2, which containssix-coordinate CuII centers. Both polymorphs form 3-D networks by virtue of aurophilic interactions of3.22007(5) Å and 3.419(3) Å, respectively, and show similar weak antiferromagnetic coupling, but havedifferent thermal decomposition temperatures. They both show vapochromic properties and, importantly,despite their significantly different solid-state structures, the vapochromic behavior of the two polymorphsis essentially identical. Upon solvent exchange, both polymorphs convert to the same Cu[Au(CN)2]2(solvent)xcomplex (solvent = H2O, CH3CN, dioxane, N,N-dimethylformamide, pyridine, NH3). The Cu[Au(CN)2]2(DMF) and Cu[Au(CN)2]2(pyridine)2 complexes have very similar 2-D square grid structures, comparableto that of 2. The solvent molecules adsorbed by Cu[Au(CN)2]2 bind to the CuII centers, thereby altering thevisible spectrum associated with the CuII chromophores and the number and frequency of the 
CN as well.The network-stabilizing gold-gold interactions and the flexible coordination sphere of CuII probably facilitatereversible solvent exchange at room temperature.
CN as well.The network-stabilizing gold-gold interactions and the flexible coordination sphere of CuII probably facilitatereversible solvent exchange at room temperature.