The Involvement of Metal-to-CO Charge Transfer and Ligand-Field Excited States in the Spectroscopy and Photochemistry of Mixed-Ligand Metal Carbonyls. A Theoretical and Spectroscopic Study of [W(CO)4(1,2-Ethylenediamine)] and [W(CO)4 (N,N''-Bis-alkyl-1,4

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F03%3A54030036" target="_blank" >RIV/61388955:_____/03:54030036 - isvavai.cz</a>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

The Involvement of Metal-to-CO Charge Transfer and Ligand-Field Excited States in the Spectroscopy and Photochemistry of Mixed-Ligand Metal Carbonyls. A Theoretical and Spectroscopic Study of [W(CO)4(1,2-Ethylenediamine)] and [W(CO)4 (N,N''-Bis-alkyl-1,4

Popis výsledku v původním jazyce

A new interpretation of the electronic spectroscopy, photochemistry, and photophysics of group 6 metal cis-tetracarbonyls [M(CO)(4)L-2] is proposed, that is based on an interplay between M-->L and M-->CO MLCT excited states. TD-DFT and resonance Raman spectroscopy show that the lowest allowed electronic transition of [W(CO)(4)(en)] (en=1,2-ethylenediamine) has a W(COeq)(2)-->COax charge-transfer character, whereby the electron density is transferred from the equatorial W(COeq)(2) moiety to pi* orbitalsof the axial CO ligands, with a net decrease of electron density on the W atom. The lowest, emissive excited state of [W(CO)(4)(en)] was identified as a spin-triplet W(COeq)(2)-->COax CT excited state both computationally and by picosecond time-resolvedIR spectroscopy. This state undergoes 1.5 ps vibrational relaxation/solvation and decays to the ground state with a similar to160 ps lifetime.

Název v anglickém jazyce

The Involvement of Metal-to-CO Charge Transfer and Ligand-Field Excited States in the Spectroscopy and Photochemistry of Mixed-Ligand Metal Carbonyls. A Theoretical and Spectroscopic Study of [W(CO)4(1,2-Ethylenediamine)] and [W(CO)4 (N,N''-Bis-alkyl-1,4

Popis výsledku anglicky

A new interpretation of the electronic spectroscopy, photochemistry, and photophysics of group 6 metal cis-tetracarbonyls [M(CO)(4)L-2] is proposed, that is based on an interplay between M-->L and M-->CO MLCT excited states. TD-DFT and resonance Raman spectroscopy show that the lowest allowed electronic transition of [W(CO)(4)(en)] (en=1,2-ethylenediamine) has a W(COeq)(2)-->COax charge-transfer character, whereby the electron density is transferred from the equatorial W(COeq)(2) moiety to pi* orbitalsof the axial CO ligands, with a net decrease of electron density on the W atom. The lowest, emissive excited state of [W(CO)(4)(en)] was identified as a spin-triplet W(COeq)(2)-->COax CT excited state both computationally and by picosecond time-resolvedIR spectroscopy. This state undergoes 1.5 ps vibrational relaxation/solvation and decays to the ground state with a similar to160 ps lifetime.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/OC%20D14.20" target="_blank" >OC D14.20: Organometalické a metalo-organické sloučeniny pro fotonické materiály</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2003

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

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Svazek periodika

125

Číslo periodika v rámci svazku

15

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

4580-4592

Kód UT WoS článku

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EID výsledku v databázi Scopus

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