Oxoclusters of the Lanthanides Begin to Resemble Solid-State Materials at Very Small Cluster Sizes: Structure and NIR Emission from Nd(III)

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• 作者：Santanu Banerjee ; G. Ajith Kumar ; Richard. E. Riman ; Thomas J. Emge ; John G. Brennan
• 刊名：Journal of the American Chemical Society
• 出版年：2007
• 出版时间：May 9, 2007
• 年：2007
• 卷：129
• 期：18
• 页码：5926 - 5931
• 全文大小：268K
• 年卷期：v.129,no.18(May 9, 2007)
• ISSN：1520-5126

文摘

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 arestacked 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 thegeometries about the oxo ions are remarkably similar to those found in solid-state Nd₂O₃. Near-IR emissionexperiments 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 compoundNd₂O₃. Intensity variations are interpreted in terms of concentration quenching and phonon relaxation.