Synthesis and characterization of copper(I) trifluoroacetate alkyne complexes of type Cu4(.mu.-O2CCF3)4(.mu.-alkyne)2 and Cu2(.mu.-O2CCF3)2(alkyne)2

Reger, Daniel L.; Huff, Mark F.

doi:10.1021/om00160a031

Cited by 25 publications

(16 citation statements)

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“…28 In this paper, we describe the reaction of trinuclear {[3,5-(CF 3 ) 2 Pz]Cu} 3 with internal alkynes to construct di-and tetranuclear copper(I) complexes with short cuprophilic contacts and a detailed photophysical and computational study of the resulting molecules. We have also included the related copper(I) trifluoroacetate 3-hexyne complexes 39 for comparison to probe the effect of pyrazole ligand support on luminescence. Some of the copper(I) adducts reported here feature bridging alkyne ligands (i.e., μ 2 −η 2 ,η 2 -alkynes).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Although copper complexes of alkynes are of significant interest as models for reaction intermediates due to their relevance in catalysis (e.g., click chemistry, cyclopropenation) 40−46 and as precursors in CVD applications, 47,48 the vast majority of the well-characterized copper-alkynes in the literature have only 2e-donor, η 2 -alkyne moieties. 45,48−52 Examples of copper(I) complexes of bridging alkynes are limited, 53 and reports involving internal alkyne ligands include Cu 2 (tropocoronand)(μ-RCCR) (R = MeCO 2 , EtCO 2 , Ph), 54,55 Cu 4 (μ-CF 3 CO 2 ) 4 (μ-EtCCEt) 2 , 39,56 Cu 4 (μ-2- 1) in ∼95% yield (Scheme 1). The synthesis of Cu 2 (μ-[3,5-(CF 3 ) 2 Pz]) 2 (EtCCEt) 2 using a mixture of 3,5-(CF 3 ) 2 PzH, Cu 2 O, and 3-hexyne has been noted in a patent on CVD precursors of copper, but only thermal analysis data were presented.…”

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis, Photophysical Properties, and Computational Analysis of Di- and Tetranuclear Alkyne Complexes of Copper(I) Supported by a Highly Fluorinated Pyrazolate

et al. 2018

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This work describes the reaction of a cyclic trinuclear complex, {[3,5-(CF 3 ) 2 Pz]Cu} 3 , with internal alkynes to construct di-and tetranuclear copper(I) complexes with short cuprophilic contacts and the study of their intriguing bonding and photophysical properties, both experimentally and theoretically. For comparison, we have also investigated the related copper(I) trifluoroacetate 3-hexyne complexes so as to deduce and isolate the role played by the supporting pyrazolate ligand on the luminescence of these and related complexes. Some adducts reported herein feature bridging (i.e., μ 2 −η 2 ,η 2 -) alkyne coordination modes, which is rare for copper(I)−alkyne complexes documented in the literature. Raman data show red shifts in the average υ ̅ CC stretching frequency from 2260 cm −1 in free 3-hexyne to 2050 cm −1 in the terminal η 2 -/2e-donor alkyne adduct Cu 2 (μ-[3,5-(CF 3 ) 2 Pz]) 2 (EtCCEt) 2 (1) and, more drastically, to 1874 cm −1 in the bridged μ 2 −η 2 ,η 2 -/4e-donor adduct Cu 4 (μ-[3,5-(CF 3 ) 2 Pz]) 4 (μ-EtCCEt) 2 (2). The tetranuclear 2-butyne adduct Cu 4 (μ-[3,5-(CF 3 ) 2 Pz]) 4 (μ-MeCCMe) 2 (3) also shows a large reduction in υ ̅ CC relative to that of free 2-butyne. The effects of strengthened copper-alkyne interactions in the bridging relative to terminal alkynes are also reflected in the CCC bending back angles. Photophysical studies in the solid state reveal the significance of the pyrazolate supporting ligand to bestow bright photoluminescence, which is found only for the pyrazolate-supported compounds 1−3 but not the trifluoroacetate copper-alkyne complexes Cu 2 (μ-CF 3 CO 2 ) 2 (EtCCEt) 2 (4) and Cu 4 (μ-CF 3 CO 2 ) 4 (μ-EtCCEt) 2 (5). The orange phosphorescence with ∼50 μs lifetime at room temperature in 1−3 thermochromically changes to generate additional green/yellow bands at cryogenic temperatures due to suppression of internal conversion from the respective T 2 → T 1 states in each solid, whereas solvent effects lead to additional blue-shifted bands in glassy solvent media. Computational analyses explains the bonding and spectral results and suggest that the major excited-state distortion is due to significant (≥20°) rotation of the alkyne ligands on Cu(I) in the di-or tetranuclear adducts, as opposed to excimeric contraction of cuprophilic Cu(I)••• Cu(I) distances. X-ray crystallographic data of 1−3 and 5 are also presented.

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Synthesis, Photophysical Properties, and Computational Analysis of Di- and Tetranuclear Alkyne Complexes of Copper(I) Supported by a Highly Fluorinated Pyrazolate

et al. 2018

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“…218, 219 Their structures are often complicated, such as polymeric systems with alkyne units that are σ‐bonded to one metal center and π‐bound to another (Scheme ). Cu I alkynyls have aroused a lot of interest due to their highly flexible bonding modes,220, 221 with common motifs including the μ 3 –η 1 type, of which the triangular Cu I alkynyls [Cu 3 (μ‐dppm) 3 (μ 3 –η 1 CCPh)] 2+ 222 and [Cu 3 (μ‐dppm) 3 (μ 3 –η 1 ‐CCPh) 2 ] + 223 are known, and those complexes where the alkyne group bridges two copper ions, that is, the Cu 2 (μ‐alkyne) unit 224. 225…”

Section: Metal Alkynyl Complexes: Cu Ag Aumentioning

confidence: 99%

The luminescent and scintillation properties of YAlO₃ and YAlO₃:Ce single crystalline films grown by liquid phase epitaxy from BaO‐based flux

Zorenko¹,

Nikl²,

Mareš³

et al. 2009

Physica Status Solidi (a)

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Single crystalline films (SCFs) of undoped and Ce 3+ -doped YAlO 3 (YAP) perovskite were crystallized by liquid-phase epitaxy method onto YAP substrates for the first time from the novel lead-free BaO-B 2 O 3 -BaF 2 fluxes. The absorption, luminescence, and scintillation properties of these films are measured and compared with the films grown from the standard PbO-B 2 O 3 flux. It appears that the films obtained from the BaObased flux exhibit better luminescent and scintillation properties with respect to films grown from the PbO-based one.

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“…[224,225] Silberalkinyle sind ebenfalls umfassend beschrieben, [44,226] und wie beim Kupfer existiert eine Serie von dreikernigen…”

Section: Metallalkinyle: Mn Reunclassified

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

Long

Williams

2003

Angewandte Chemie

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Metallalkinylkomplexe bergen eine große Anziehungskraft für die Synthesechemie, die Strukturchemie und die Materialwissenschaften, sodass mittlerweile eine Vielzahl von Reaktionen zur M‐CC‐Verknüpfung mit einer ganzen Skala von Übergangsmetall‐ und Alkinylreagentien entwickelt wurde. Einige Methoden sind breit anwendbar, andere beschränken sich auf ein spezielles Metall oder Substrat. Wegen der linearen Geometrie der Alkinyleinheit und ihrem ungesättigten Charakter sind die Metallalkinyle attraktive Bausteine für molekulare Drähte und polymere metallorganische Materialien, die interessante physikalische Eigenschaften wie flüssigkristallines Verhalten, optische Nichtlinearität, Lumineszenz und elektrische Leitfähigkeit aufweisen können. Dieses einzigartige Spektrum an Eigenschaften steht als treibende Kraft hinter der intensiven Erforschung von Metall‐Alkinyl‐σ‐Komplexen. Die Entwicklung und Fortschritte insbesondere der letzten zehn Jahre werden in diesem Aufsatz zusammengefasst.

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Synthesis and characterization of copper(I) trifluoroacetate alkyne complexes of type Cu4(.mu.-O2CCF3)4(.mu.-alkyne)2 and Cu2(.mu.-O2CCF3)2(alkyne)2

Cited by 25 publications

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Synthesis, Photophysical Properties, and Computational Analysis of Di- and Tetranuclear Alkyne Complexes of Copper(I) Supported by a Highly Fluorinated Pyrazolate

Synthesis, Photophysical Properties, and Computational Analysis of Di- and Tetranuclear Alkyne Complexes of Copper(I) Supported by a Highly Fluorinated Pyrazolate

The luminescent and scintillation properties of YAlO₃ and YAlO₃:Ce single crystalline films grown by liquid phase epitaxy from BaO‐based flux

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

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Synthesis and characterization of copper(I) trifluoroacetate alkyne complexes of type Cu4(.mu.-O2CCF3)4(.mu.-alkyne)2 and Cu2(.mu.-O2CCF3)2(alkyne)2

Cited by 25 publications

References 0 publications

Synthesis, Photophysical Properties, and Computational Analysis of Di- and Tetranuclear Alkyne Complexes of Copper(I) Supported by a Highly Fluorinated Pyrazolate

Synthesis, Photophysical Properties, and Computational Analysis of Di- and Tetranuclear Alkyne Complexes of Copper(I) Supported by a Highly Fluorinated Pyrazolate

The luminescent and scintillation properties of YAlO3 and YAlO3:Ce single crystalline films grown by liquid phase epitaxy from BaO‐based flux

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

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The luminescent and scintillation properties of YAlO₃ and YAlO₃:Ce single crystalline films grown by liquid phase epitaxy from BaO‐based flux