The first perfluoroacetylacetonate metal complexes: as unexpectedly robust as tricky to makeElectronic supplementary information (ESI) available: details of the preparation of the complexes, analytical, NMR spectroscopical, and crystallographic data. See: http://www.rsc.org/suppdata/cc/b1/b111249j/

Петров, В. А.; Marshall, William J.; Grushin, Vladimir V.

doi:10.1039/b111249j

Cited by 35 publications

(4 citation statements)

References 5 publications

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“…Average F7-acac oxygen-lanthanide(III) bond distances are 2.409(5) Å (6), 2.394(4) Å (7), 2.338(4) Å (9) and 2.317(4) Å (10) and follow the 8-coordinate lanthanide contraction as the series is progressed. Similarly, the average (Ar F )3PO-Ln 3+ distances become smaller traversing the 4f series (2.368(5) Å for 6 to 2.269(4) Å for 10) and lie in the range of those reported previously for the complex [Er(F7-acac)3{(Ar F )3PO}2] which is a polymorph of 9 [47] and for the related complex [Eu(F7-acac)3{Ph3PO}2] [49].…”

Section: Single Crystal X-ray Diffraction Analysissupporting

confidence: 79%

Optical Properties of Heavily Fluorinated Lanthanide Tris β-Diketonate Phosphine Oxide Adducts

et al. 2016

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The construction of lanthanide(III) chelates that exhibit superior photophysical properties holds great importance in biological and materials science. One strategy to increase the luminescence properties of lanthanide(III) chelates is to hinder competitive non-radiative decay processes through perfluorination of the chelating ligands. Here, the synthesis of two families of heavily fluorinated lanthanide(III) β-diketonate complexes bearing monodentate perfluorinated tris phenyl phosphine oxide ligands have been prepared through a facile one pot reaction [Ln(hfac) 3 {(Ar F) 3 PO}(H 2 O)] and [Ln(F 7-acac) 3 {(Ar F) 3 PO} 2 ] (where Ln = Sm 3+ , Eu 3+ , Tb 3+ , Er 3+ and Yb 3+). Single crystal X-ray diffraction analysis in combination with photophysical studies have been performed to investigate the factors responsible for the differences in the luminescence lifetimes and intrinsic quantum yields of the complexes. Replacement of both bound H 2 O and C-H oscillators in the ligand backbone has a dramatic effect on the photophysical properties of the complexes, particularly for the near infra-red emitting ion Yb 3+ , where a five fold increase in luminescence lifetime and quantum yield is observed. The complexes [Sm(hfac) 3 {(Ar F) 3 PO}(H 2 O)] (1), [Yb(hfac) 3 {(Ar F) 3 PO}(H 2 O)] (5), [Sm(F 7-acac) 3 {(Ar F) 3 PO} 2 ] (6) and [Yb(F 7-acac) 3 {(Ar F) 3 PO} 2 ] (10) exhibit unusually long luminescence lifetimes and attractive intrinsic quantum yields of emission in fluid solution (Φ Ln = 3.4% (1); 1.4% (10)) and in the solid state (Φ Ln = 8.5% (1); 2.0% (5); 26% (6); 11% (10)), which are amongst the largest values for this class of compounds to date.

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Section: Single Crystal X-ray Diffraction Analysissupporting

confidence: 79%

Optical Properties of Heavily Fluorinated Lanthanide Tris β-Diketonate Phosphine Oxide Adducts

et al. 2016

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“…[Cu(L2) 2 ], which bears perfluorinated acac ligands, is much less active, probably due to ligand fragmentation (Table 1, entries 9 and 10). [19] Because [CuA C H T U N G T R E N N U N G (hfacac) 2 ] is highly active and commercially available, we chose to use this catalyst to study the diene scope (Scheme 2). A wide range of mono-, di-, and trisubstituted conjugated dienes gave the target [4+1] cycloadducts.…”

Section: Resultsmentioning

confidence: 99%

An Efficient, Overall [4+1] Cycloadditon of 1,3‐Dienes and Nitrene Precursors

Ren

et al. 2011

Chemistry A European J

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Intermolecular cycloadditions of conjugated dienes and nitrene precursors usually produce aziridines. A generally useful method was lacking to directly provide the [4+1] cycloadducts, 3-pyrrolines. We have realized this transformation by using an uniquely active catalyst, copper(II) 1,1,1,5,5,5-hexafluoroacetylacetonate ([Cu(hfacac)(2)]). The method is applicable to a wide array of dienes with good yields. When 1,4-disubstituted dienes are used as substrates, good-to-excellent cis or trans selectivity can be obtained. Interestingly, the cis or trans preference depends on the nature of the substituents, rather than diene geometry. Mechanistic studies reveal that the [4+1] cycloaddition proceeds through diene aziridination and subsequent ring expansion. Among common copper catalysts, only [Cu(hfacac)(2)] can efficiently catalyze both steps, which explains the unique efficiency of the catalyst.

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“…Considering that and the large size of the Pt−M (eq 81) and Pd−M rings, it is conceivable that the products might in fact be oligomeric or polymeric species. The most recently described Pd−Eu dppeO material was indeed formulated as a polymer (eq 82) …”

Section: 2 Heteropolymetallic Complexesmentioning

confidence: 99%

Mixed Phosphine−Phosphine Oxide Ligands

2004

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The first perfluoroacetylacetonate metal complexes: as unexpectedly robust as tricky to makeElectronic supplementary information (ESI) available: details of the preparation of the complexes, analytical, NMR spectroscopical, and crystallographic data. See: http://www.rsc.org/suppdata/cc/b1/b111249j/

Abstract: First metal complexes containing the perfluoroacetylacetonato ligand have been prepared by the reaction of anhydrous Ln(OAc)3 (Ln = Eu, Tb, Tm) with heptafluoroacetylacetone, optionally in the presence of other ligands Ph3PO, bpy, and PyO.

Cited by 35 publications

References 5 publications

Optical Properties of Heavily Fluorinated Lanthanide Tris β-Diketonate Phosphine Oxide Adducts

Optical Properties of Heavily Fluorinated Lanthanide Tris β-Diketonate Phosphine Oxide Adducts

An Efficient, Overall [4+1] Cycloadditon of 1,3‐Dienes and Nitrene Precursors

Mixed Phosphine−Phosphine Oxide Ligands

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