Batrice Rami J, Ayscue R Lee, Adcock Alyssa K, Sullivan Benjamin R, Han Sae Young, Piccoli Philip M, Bertke Jeffery A, Knope Karah E
Department of Chemistry, Georgetown University, 37th and O Sts. NW, Washington, DC, 20057, USA.
Department of Geology, University of Maryland, College Park, MD, 20742, USA.
Chemistry. 2018 Apr 11;24(21):5630-5636. doi: 10.1002/chem.201706143. Epub 2018 Mar 13.
A bismuth-organic compound containing 2,2':6'2"-terpyridine (terpy) and 2-thiophenecarboxylate (TC), of the general formula (terpy)Bi(κ -TC) ⋅0.47 H O (BiOM-1), has been synthesized under hydrothermal conditions. Addition of a lanthanide nitrate solution to the reaction mixture led to statistical replacement of the bismuth centers, and yielded isomorphous lanthanide containing compounds Bi Ln OM-1 (Ln=Nd, Sm, Eu, Tb, Dy, Er, and Yb) that showed bismuth and/or ligand sensitized lanthanide-centered emission, and the first example of NIR emission from a lanthanide doped BiOM. The structure was determined by single-crystal X-ray diffraction, and the level and uniformity of lanthanide ion incorporation into the bismuth host was determined by ICP-OES and electron microprobe analysis. For the visible emitters, lifetime data and quantum yields are presented. A high efficiency of sensitization was calculated for the europium analog (50.1 %), showing significant improvement over previously reported europium thiophenecarboxylates. These novel materials may provide strategies to address concerns over the long-term sustainability of the rare earth elements, especially relating to optical devices.
在水热条件下合成了一种含2,2':6'2"-三联吡啶（terpy）和2-噻吩甲酸酯（TC）的铋有机化合物，其通式为(terpy)Bi(κ -TC) ⋅0.47 H₂O（BiOM-1）。向反应混合物中加入硝酸镧溶液会导致铋中心的统计性取代，并生成同构的含镧系元素化合物BiLnOM-1（Ln = Nd、Sm、Eu、Tb、Dy、Er和Yb），这些化合物表现出铋和/或配体敏化的以镧系元素为中心的发射，并且是掺杂镧系元素的BiOM产生近红外发射的首个实例。通过单晶X射线衍射确定了结构，并通过电感耦合等离子体发射光谱法（ICP-OES）和电子微探针分析确定了镧系离子掺入铋主体中的水平和均匀性。对于可见光发射体，给出了寿命数据和量子产率。计算出铕类似物的敏化效率很高（50.1 %），与先前报道的铕噻吩甲酸盐相比有显著提高。这些新型材料可能为解决稀土元素长期可持续性问题提供策略，特别是与光学器件相关的问题。
