Charakterizace a dynamika excitovaných stavů [W(CO)5(4-kyanopyridin)] a [W(CO)5(piperidin)] studovaná pikosekundovou časově rozlišenou IR a resonanční Ramanovou spektroskopií a DFT výpočty

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F04%3A00101038" target="_blank" >RIV/61388955:_____/04:00101038 - 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

Excited State Characters and Dynamics of [W(CO)5(4-cyanopyridine)] and [W(CO)5(piperidine)] Studied by Picosecond Time-Resolved IR and Resonance Raman Spectroscopy and DFT Calculations. Roles of W -> L, and W -> CO MLCT and LF Excited States Revised

Popis výsledku v původním jazyce

The character, dynamics and relaxation pathways of low-lying excited states of the complexes [W(CO)5L]; L = 4-CN-pyridine (pyCN) and piperidine (pip) were investigated by a combined theoretical and spectroscopic study. DFT and TD-DFT calculations revealed the delocalized character of chemically and spectroscopicaly relevant molecular orbitals and the presence of a manifold of low-lying CO .sigma.* - based unoccupied molecular orbitals. Traditional ligand-field arguments are not applicable. The lowest excited states of [W(CO)5(pyCN)] are W-pyCN MLCT in character, denoted MLCT(pyCN). They are closely followed in energy by W-CO MLCT states, MLCT(CO). Calculated changes of electron density distribution upon MLCT(pyCN) excitation show that the electron density is transferred from the whole W(CO)5 fragment to the pyCN ligand and highlight the electron-accepting role of the CN group. Optical excitation at 400 or 500 nm leads to population of a 3MLCT(pyCN).

Název v anglickém jazyce

Excited State Characters and Dynamics of [W(CO)5(4-cyanopyridine)] and [W(CO)5(piperidine)] Studied by Picosecond Time-Resolved IR and Resonance Raman Spectroscopy and DFT Calculations. Roles of W -> L, and W -> CO MLCT and LF Excited States Revised

Popis výsledku anglicky

The character, dynamics and relaxation pathways of low-lying excited states of the complexes [W(CO)5L]; L = 4-CN-pyridine (pyCN) and piperidine (pip) were investigated by a combined theoretical and spectroscopic study. DFT and TD-DFT calculations revealed the delocalized character of chemically and spectroscopicaly relevant molecular orbitals and the presence of a manifold of low-lying CO .sigma.* - based unoccupied molecular orbitals. Traditional ligand-field arguments are not applicable. The lowest excited states of [W(CO)5(pyCN)] are W-pyCN MLCT in character, denoted MLCT(pyCN). They are closely followed in energy by W-CO MLCT states, MLCT(CO). Calculated changes of electron density distribution upon MLCT(pyCN) excitation show that the electron density is transferred from the whole W(CO)5 fragment to the pyCN ligand and highlight the electron-accepting role of the CN group. Optical excitation at 400 or 500 nm leads to population of a 3MLCT(pyCN).

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

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2004

Kód důvěrnosti údajů

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

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

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Svazek periodika

43

Číslo periodika v rámci svazku

5

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

1723-1734

Kód UT WoS článku

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EID výsledku v databázi Scopus

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