Oxoclusters of the lanthanides begin to resemble solid-state materials at very small cluster sizes: Structure and NIR emission from Nd(III)

Santanu Banerjee; G. Ajith Kumar; Richard E. Riman; Thomas J. Emge; John G. Brennan

doi:https://doi.org/10.1021/ja069000a

Oxoclusters of the lanthanides begin to resemble solid-state materials at very small cluster sizes: Structure and NIR emission from Nd(III)

Santanu Banerjee, G. Ajith Kumar, Richard E. Riman, Thomas J. Emge, John G. Brennan

Rutgers, The State University

Research output: Contribution to journal › Article › peer-review

34 Scopus citations

Abstract

The reaction of Nd(SePh)₃ with SeO₂ and Hg in pyridine gives the dodecanuclear cluster [(py)₁₈Nd₁₂O ₆Se₄(Se₂)₄(SePh)₄(Se ₂Ph)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 Nd ₂O₃. 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.

Original language	English (US)
Pages (from-to)	5926-5931
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	129
Issue number	18
DOIs	https://doi.org/10.1021/ja069000a
State	Published - May 9 2007

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Oxoclusters of the lanthanides begin to resemble solid-state materials at very small cluster sizes: Structure and NIR emission from Nd(III)",

abstract = "The reaction of Nd(SePh)3 with SeO2 and Hg in pyridine gives the dodecanuclear cluster [(py)18Nd12O 6Se4(Se2)4(SePh)4(Se 2Ph)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 Nd 2O3. 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.",

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T2 - Structure and NIR emission from Nd(III)

AU - Banerjee, Santanu

AU - Kumar, G. Ajith

AU - Riman, Richard E.

AU - Emge, Thomas J.

AU - Brennan, John G.

PY - 2007/5/9

Y1 - 2007/5/9

N2 - The reaction of Nd(SePh)3 with SeO2 and Hg in pyridine gives the dodecanuclear cluster [(py)18Nd12O 6Se4(Se2)4(SePh)4(Se 2Ph)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 Nd 2O3. 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.

AB - The reaction of Nd(SePh)3 with SeO2 and Hg in pyridine gives the dodecanuclear cluster [(py)18Nd12O 6Se4(Se2)4(SePh)4(Se 2Ph)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 Nd 2O3. 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.

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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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