Solid‐State Structure, Quantum Calculations and Spectroscopic Characterization of the Hydrogen‐Bonded Complex [Os(bpy)2(CO)(EtO···H‐DMAP)][PF6]2

Garino, Claudio; Gobetto, Roberto; Nervi, Carlo; Salassa, Luca; Croce, Gianluca; Milanesio, Marco; Rosenberg, Edward; Ross, J. B. Alexander

doi:10.1002/ejic.200400631

Cited by 7 publications

(1 citation statement)

References 65 publications

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“…The structure resulted in being ordered, also in the PF 6 − anion, that was often found to be disordered in similar structures. [35][36][37] Relevant XRD data are reported in the ESI. † The crystal structure was deposited into CCDC with reference number 1452806.…”

Section: Crystallographic Characterizationmentioning

confidence: 99%

Origin of a counterintuitive yellow light-emitting electrochemical cell based on a blue-emitting heteroleptic copper(i) complex

et al. 2016

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a This work provides the synthesis, structural characterization, electrochemical and photophysical features, as well as the application in light-emitting electrochemical cells (LECs) of a novel heteroleptic copper(I) complex -[Cu(impy)(POP)] [PF 6 ], where impy is 3-(2-methoxyphenyl)-1-(pyridine-2-yl)imidazo[1,5-a]pyridine and POP is bis{2-(diphenylphosphanyl)phenyl}ether. This compound shows blue photoluminescence (PL, λ = 450 nm) in solution and solid-state and excellent redox stability. Despite these excellent features, the electroluminescence (EL) response is located at ∼550 nm. Although the EL spectrum of LECs is typically red-shifted compared to the PL of the electroluminescent material, a shift of ca. 100 nm represents the largest one reported in LECs. To date, the large shift phenomena have been attributed to (i) a change in the nature of the lowest emitting state due to a concentration effect of the films, (ii) a reversible substitution of the ligands due to the weak coordination to the Cu(I), and (iii) a change in the distribution of the excited states due to polarization effects. After having discarded these along with others like the irreversible degradation of the emitter during device fabrication and/or under operation conditions, driving conditions, active layer composition, and changes in the excited states under different external electrical stimuli, we attribute the origin of this unexpected shift to a lack of a thermally activated delayed fluorescence (TADF) process due to the solely ligand-centered character of the excited states. As such, the lack of a charge transfer character in the excited states leads to a blue-fluorescence and yellowphosphorescence photo-and electro-responses, respectively. This corroborates recent studies focused on the design of TADF for heteroleptic copper(I) complexes. Overall, this work is a clear insight into the design of new copper(I) complexes towards the preparation of blue LECs, which are still unexplored.

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Section: Crystallographic Characterizationmentioning

confidence: 99%

Origin of a counterintuitive yellow light-emitting electrochemical cell based on a blue-emitting heteroleptic copper(i) complex

et al. 2016

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Chiral and Nonchiral [OsX₂(diphosphane)(diamine)] (X: Cl, OCH₂CF₃) Complexes for Fast Hydrogenation of Carbonyl Compounds

Baratta

Barbato

Magnolia

et al. 2010

Chemistry A European J

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The osmium complexes trans-[OsCl(2)(dppf)(diamine)] (dppf: 1,1'-bis(diphenylphosphino)ferrocene; diamine: ethylenediamine in 3, propylenediamine in 4) were prepared by the reaction of [OsCl(2)(PPh(3))(3)] (1) with the ferrocenyl diphosphane, dppf and the corresponding diamine in dichloromethane. The reaction of derivative 3 with NaOCH(2)CF(3) in toluene afforded the alkoxide cis-[Os(OCH(2)CF(3))(2)(dppf)(ethylenediamine)] (5). The novel precursor [Os(2)Cl(4)(P(m-tolyl)(3))(5)] (2) allows the synthesis of the chiral complexes trans-[OsCl(2)(diphosphane)(1,2-diamine)] (6-9; diphosphane: (R)-[6,6'-dimethoxy(1,1'-biphenyl)-2,2'-diyl]bis[1,1-bis(3,5-dimethylphenyl)phosphane] (xylMeObiphep) or (R)-(1,1'-binaphthalene)-2,2'-diylbis[1,1-bis(3,5-dimethylphenyl)phosphane] (xylbinap); diamine=(R,R)-1,2-diphenylethylenediamine (dpen) or (R,R)-1,2-diaminocyclohexane (dach)), obtained by the treatment of 2 with the diphosphane and the 1,2-diamine in toluene at reflux temperature. Compounds 3-5 in ethanol and in the presence of NaOEt catalyze the reduction of methyl aryl, dialkyl, and diaryl ketones and aldehydes with H(2) at low pressure (5 atm), with substrate/catalyst (S/C) ratios of 10,000-200,000 and achieving turnover frequencies (TOFs) of up to 3.0 x 10(5) h(-1) at 70 degrees C. By employment of the chiral compounds 6-9, different ketones, including alkyl aryl, bulky tert-butyl, and cyclic ketones, have successfully been hydrogenated with enantioselectivities up to 99% and with S/C ratios of 5000-100,000 and TOFs of up to 4.1 x 10(4) h(-1) at 60 degrees C.

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Synthesis, Electrochemical and Electrogenerated Chemiluminescence Studies of Ruthenium(II) Bis(2,2′‐bipyridyl){2‐(4‐methylpyridin‐2‐yl)benzo[d]‐X‐azole} Complexes

et al. 2006

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A series of photoactive complexes of [Ru II bis(bipyridyl){2-(4-methylpyridin-2-yl)benzo[d]-X-azole}](PF 6 ) 2 (X = N-CH 3 , 1; S, 2; or O, 3) have been synthesized and fully characterized by proton and 13 C NMR spectroscopy and UV/Vis spectroscopy. The X-ray structure of 1 is also reported. The electrochemical behavior and the photophysical properties of 1-3 have been investigated. Cyclic voltammetry (CV) reveals the presence of three consecutive one-electron reduction processes and a single one-electron oxidation process that

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Solid‐State Structure, Quantum Calculations and Spectroscopic Characterization of the Hydrogen‐Bonded Complex [Os(bpy)₂(CO)(EtO···H‐DMAP)][PF₆]₂

Cited by 7 publications

References 65 publications

Origin of a counterintuitive yellow light-emitting electrochemical cell based on a blue-emitting heteroleptic copper(i) complex

Origin of a counterintuitive yellow light-emitting electrochemical cell based on a blue-emitting heteroleptic copper(i) complex

Chiral and Nonchiral [OsX₂(diphosphane)(diamine)] (X: Cl, OCH₂CF₃) Complexes for Fast Hydrogenation of Carbonyl Compounds

Synthesis, Electrochemical and Electrogenerated Chemiluminescence Studies of Ruthenium(II) Bis(2,2′‐bipyridyl){2‐(4‐methylpyridin‐2‐yl)benzo[d]‐X‐azole} Complexes

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Solid‐State Structure, Quantum Calculations and Spectroscopic Characterization of the Hydrogen‐Bonded Complex [Os(bpy)2(CO)(EtO···H‐DMAP)][PF6]2

Cited by 7 publications

References 65 publications

Origin of a counterintuitive yellow light-emitting electrochemical cell based on a blue-emitting heteroleptic copper(i) complex

Origin of a counterintuitive yellow light-emitting electrochemical cell based on a blue-emitting heteroleptic copper(i) complex

Chiral and Nonchiral [OsX2(diphosphane)(diamine)] (X: Cl, OCH2CF3) Complexes for Fast Hydrogenation of Carbonyl Compounds

Synthesis, Electrochemical and Electrogenerated Chemiluminescence Studies of Ruthenium(II) Bis(2,2′‐bipyridyl){2‐(4‐methylpyridin‐2‐yl)benzo[d]‐X‐azole} Complexes

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Solid‐State Structure, Quantum Calculations and Spectroscopic Characterization of the Hydrogen‐Bonded Complex [Os(bpy)₂(CO)(EtO···H‐DMAP)][PF₆]₂

Chiral and Nonchiral [OsX₂(diphosphane)(diamine)] (X: Cl, OCH₂CF₃) Complexes for Fast Hydrogenation of Carbonyl Compounds