The phototransfer of an electron in manganese (III) tris-acetylacetonate and bis-acetylacetonatotrifluoroacetate

Kryukov, A. I.; Tkachenko, Z. A.; Bukhtiyarov, V.K.; Kriss, E.E.

doi:10.1007/bf00522423

Cited by 3 publications

(5 citation statements)

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“…The multiple d–d electronic transitions, accessible with a single-wavelength excitation, are predicted at wavelengths of ca. 500 nm for these manganese complexes . The fluorescence emissions from Mn II bis(acetylacetonate) and Ni II bis(acetylacetonate) are weaker than that from Mn III tris(acetylacetonate) because the d–d transition is spin-forbidden and the d–d transition at 650 nm has low quantum yield, respectively .…”

Section: Results and Discussionmentioning

confidence: 92%

“…Transition-metal acetylacetonate (acac) complexes constitute a class of such fluorescent complexes, which are likely the source of fluorescence in Li-ion systems. In fact, the peculiar properties of distorted octahedral Ni II , Mn II , and Mn III acac complexes have been extensively studied for many decades. − The trimeric Ni II bis(acetylacetonate), Mn II bis(acetylacetonate), and Mn III tris(acacetylacetonate) complexes display strong geometric distortions along the x , y , and z axes, respectively, leading to splitting of the originally fivefold-degenerate 3d orbitals into five distinct levels. The multiple d–d electronic transitions, accessible with a single-wavelength excitation, are predicted at wavelengths of ca.…”

Section: Results and Discussionmentioning

confidence: 99%

“…500 nm for these manganese complexes. 37 The fluorescence emissions from Mn II bis(acetylacetonate) and Ni II bis(acetylacetonate) are weaker than that from Mn III tris(acetylacetonate) because the d−d transition is spin-forbidden and the d−d transition at 650 nm has low quantum yield, respectively. 40 Importantly for this investigation of Li-ion systems, those metal complexes are stable and soluble in carbonate ester solvents.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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The Formation Mechanism of Fluorescent Metal Complexes at the Li_xNi_0.5Mn_1.5O_4−δ/Carbonate Ester Electrolyte Interface

et al. 2015

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Electrochemical oxidation of carbonate esters at the Li(x)Ni(0.5)Mn(1.5)O(4-δ)/electrolyte interface results in Ni/Mn dissolution and surface film formation, which negatively affect the electrochemical performance of Li-ion batteries. Ex situ X-ray absorption (XRF/XANES), Raman, and fluorescence spectroscopy, along with imaging of Li(x)Ni(0.5)Mn(1.5)O(4-δ) positive and graphite negative electrodes from tested Li-ion batteries, reveal the formation of a variety of Mn(II/III) and Ni(II) complexes with β-diketonate ligands. These metal complexes, which are generated upon anodic oxidation of ethyl and diethyl carbonates at Li(x)Ni(0.5)Mn(1.5)O(4-δ), form a surface film that partially dissolves in the electrolyte. The dissolved Mn(III) complexes are reduced to their Mn(II) analogues, which are incorporated into the solid electrolyte interphase surface layer at the graphite negative electrode. This work elucidates possible reaction pathways and evaluates their implications for Li(+) transport kinetics in Li-ion batteries.

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Section: Results and Discussionmentioning

confidence: 92%

Section: Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

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The Formation Mechanism of Fluorescent Metal Complexes at the Li_xNi_0.5Mn_1.5O_4−δ/Carbonate Ester Electrolyte Interface

et al. 2015

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“…The N-bonded thiocyanate ligand is oxidised to the SCN radical which can be spin trapped and Mo(V1) is reduced to Mo(V). Kryukov et al (1983) have also shown reduction of the metal ion and oxidation of both the ligand and ethanol solvent in the UV-irradiation of Mnlll(acac)g and Mn"'(a~ac)~0COCF3. Finally, Buckels and Wasgestian (1983) have demonstrated that in oxidative p.e.t.…”

Section: Organic Compoundsmentioning

confidence: 93%

PHOTOCHEMICAL ELECTRON TRANSFER REACTIONS and EXCIPLEXES

Creed

Caldwell

1985

Photochem & Photobiology

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“…The neutral Mn(acac) 2,3 molecules in solution were successfully investigated earlier, − but the singly coordinated Mn(acac) 1 has never been observed in solution. Here, we show that the low-coordinated Mn(acac) 1 + complex can be accessed in the gas phase.…”

Section: Introductionmentioning

confidence: 99%

Electronic Structure of the Complete Series of Gas-Phase Manganese Acetylacetonates by X-ray Absorption Spectroscopy

Ablyasova,

Guo,

Zamudio-Bayer

et al. 2023

J. Phys. Chem. A

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Metal centers in transition metal–ligand complexes occur in a variety of oxidation states causing their redox activity and therefore making them relevant for applications in physics and chemistry. The electronic state of these complexes can be studied by X-ray absorption spectroscopy, which is, however, due to the complex spectral signature not always straightforward. Here, we study the electronic structure of gas-phase cationic manganese acetylacetonate complexes Mn(acac)1–3 + using X-ray absorption spectroscopy at the metal center and ligand constituents. The spectra are well reproduced by multiconfigurational wave function theory, time-dependent density functional theory as well as parameterized crystal field and charge transfer multiplet simulations. This enables us to get detailed insights into the electronic structure of ground-state Mn(acac)1–3 + and extract empirical parameters such as crystal field strength and exchange coupling from X-ray excitation at both the metal and ligand sites. By comparison to X-ray absorption spectra of neutral, solvated Mn(acac)2,3 complexes, we also show that the effect of coordination on the L3 excitation energy, routinely used to identify oxidation states, can contribute about 40–50% to the observed shift, which for the current study is 1.9 eV per oxidation state.

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The phototransfer of an electron in manganese (III) tris-acetylacetonate and bis-acetylacetonatotrifluoroacetate

Cited by 3 publications

References 5 publications

The Formation Mechanism of Fluorescent Metal Complexes at the Li_xNi_0.5Mn_1.5O_4−δ/Carbonate Ester Electrolyte Interface

The Formation Mechanism of Fluorescent Metal Complexes at the Li_xNi_0.5Mn_1.5O_4−δ/Carbonate Ester Electrolyte Interface

PHOTOCHEMICAL ELECTRON TRANSFER REACTIONS and EXCIPLEXES

Electronic Structure of the Complete Series of Gas-Phase Manganese Acetylacetonates by X-ray Absorption Spectroscopy

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The phototransfer of an electron in manganese (III) tris-acetylacetonate and bis-acetylacetonatotrifluoroacetate

Cited by 3 publications

References 5 publications

The Formation Mechanism of Fluorescent Metal Complexes at the LixNi0.5Mn1.5O4−δ/Carbonate Ester Electrolyte Interface

The Formation Mechanism of Fluorescent Metal Complexes at the LixNi0.5Mn1.5O4−δ/Carbonate Ester Electrolyte Interface

PHOTOCHEMICAL ELECTRON TRANSFER REACTIONS and EXCIPLEXES

Electronic Structure of the Complete Series of Gas-Phase Manganese Acetylacetonates by X-ray Absorption Spectroscopy

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Product

Resources

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The Formation Mechanism of Fluorescent Metal Complexes at the Li_xNi_0.5Mn_1.5O_4−δ/Carbonate Ester Electrolyte Interface

The Formation Mechanism of Fluorescent Metal Complexes at the Li_xNi_0.5Mn_1.5O_4−δ/Carbonate Ester Electrolyte Interface