Banerjee Santanu, Kumar G Ajith, Riman Richard E, Emge Thomas J, Brennan John G
Department of Chemistry and Chemical Biology, the State University of New Jersey, Piscataway, New Jersey 08854-8087, USA.
J Am Chem Soc. 2007 May 9;129(18):5926-31. doi: 10.1021/ja069000a. Epub 2007 Apr 18.
The reaction of Nd(SePh)3 with SeO2 and Hg in pyridine gives the dodecanuclear cluster [(py)18Nd12O6Se4(Se2)4(SePh)4(Se2Ph)2Hg2(SePh)4][(Hg(SePh)3]2. In this compound the 12 Nd(III) ions are stacked in four sets of Nd3, with pairs of tetrahedral oxo ligands separating the Nd3 planes and Se, SeSe, SePh, pyridine, and HgSePh groups encapsulating the oxo core. Both the Nd-O bond lengths and the geometries about the oxo ions are remarkably similar to those found in solid-state Nd2O3. Near-IR emission experiments indicate that the cluster emission properties are less intense than those of highly emissive (DME)2Nd(SC6F5)3 or (THF)8Nd8O2Se2(SePh)16 but brighter than the nonemissive solid-state compound Nd2O3. Intensity variations are interpreted in terms of concentration quenching and phonon relaxation.
Nd(SePh)₃与SeO₂和Hg在吡啶中反应生成十二核簇合物[(py)₁₈Nd₁₂O₆Se₄(Se₂)₄(SePh)₄(Se₂Ph)₂Hg₂(SePh)₄][(Hg(SePh)₃]₂。在该化合物中，12个Nd(III)离子堆积成四组Nd₃，成对的四面体氧配体分隔Nd₃平面，Se、SeSe、SePh、吡啶和HgSePh基团包裹着氧核心。Nd - O键长和氧离子周围的几何结构与固态Nd₂O₃中的非常相似。近红外发射实验表明，该簇合物的发射性质不如高发射性的(DME)₂Nd(SC₆F₅)₃或(THF)₈Nd₈O₂Se₂(SePh)₁₆强烈，但比无发射的固态化合物Nd₂O₃亮。强度变化用浓度猝灭和声子弛豫来解释。
