Structure and Emissive Properties of Heterobimetallic Ln鈥揂u Coordination Polymers: Role of Tb and Eu in Non-aurophilic [nBu4N]2[Ln(NO3)4Au(CN)
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- 作者：John C. Ahern ; Ryan J. Roberts ; Philip Follansbee ; Jeffrey McLaughlin ; Daniel B. Leznoff ; Howard H. Patterson
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：July 21, 2014
- 年：2014
- 卷：53
- 期：14
- 页码：7571-7579
- 全文大小：389K
- ISSN：1520-510X
文摘
This investigation is focused on comparing photophysical properties between two series of lanthanide-dicyanoaurate coordination polymers that contain and lack aurophilic interactions, respectively. Luminescence and crystallographic studies have been carried out on five different coordination polymer chain frameworks: the non-aurophilic [nBu4N]2[LnxGd1鈥?i>x(NO3)4Au(CN)2] (Ln = Eu, Tb; x = 0.01, 0.02, 0.04, 0.08) and[nBu4N]2[EuxTb1鈥?i>x(NO3)4Au(CN)2] (x = 0.25, 0.5, 0.75), as well as the analogous solid-solutions of aurophilic LnxGd1鈥?i>x[Au(CN)2]3路3H2O and EuxTb1鈥?i>x[Au(CN)2]3路3H2O. The single-crystal structures of M[Au(CN)2]3 路3H2O (M = Eu, Gd) are also reported for comparison. In the aurophilic frameworks the close proximity of gold(I) centers on neighboring chains allows for Au鈥揂u interactions to take place that facilitate energy transfer between lanthanides. Terbium- and europium-doped aurophilic frameworks show energy transfer between one of the lanthanide ions and dicyanoaurate centers as observed via luminescence measurements. In the non-aurophilic frameworks the [nBu4N] cations separate the Au鈥揂u chains, thereby preventing interaction between them, and preventing energy transfer. By preparing the aurophilic EuxTb1鈥?i>x[Au(CN)2]3路3D2O frameworks, it was shown that the O鈥揌 vibrational energy in the hydrated (aurophilic) samples can partially quench the Ln signal.