Ultrafast Photochemical Dissociation of an Equatorial CO Ligand from trans(X,X)-[Ru(X)2(CO)2(bpy)] (X = Cl, Br, I). A Picosecond Time-Resolved Infrared Spectroscopic and DFT Computational Study
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F04%3A00107649" target="_blank" >RIV/61388955:_____/04:00107649 - isvavai.cz</a>
Result on the web
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DOI - Digital Object Identifier
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Alternative languages
Result language
angličtina
Original language name
Ultrafast Photochemical Dissociation of an Equatorial CO Ligand from trans(X,X)-[Ru(X)2(CO)2(bpy)] (X = Cl, Br, I). A Picosecond Time-Resolved Infrared Spectroscopic and DFT Computational Study
Original language description
Ultrafast photochemistry of the complexes trans(X,X)-[Ru(X)2(CO)2(bpy)] (X = Cl, Br, I) was studied in order to understand excited-state reactivity of an equatorial CO ligand, which is coordinated trans to the 2,2''-bipyridine ligand (bpy). TD-DFT calculations have identified the lowest electronic transitions and singlet excited states as mixed X->bpy/Ru->bpy ligand to ligand and metal to ligand charge transfer (LLCT/MLCT). Picosecond time-resolved IR spectroscopy in the region of v(CO) vibrations has revealed that the CO dissociation is sub-picosecond for X = Cl and Br, producing a pentacoordinated intermediate trans(X,X)-[Ru(X)2(CO)(bpy)]. Movement of an axial halide ligand to the vacant equatorial position and solvent (CH3CN) coordination follows with a time constant of 13-15 ps.
Czech name
Ultrarychlá fotochemická disociace ekvatoriálního CO ligandu z trans(X,X)-[Ru(X)2(CO)2(bpy)] (X = Cl, Br, I). Pikosekundová infračervená spektroskopie a DFT výpočetní studie
Czech description
Ultrarychlá fotochemie komplexů trans(X,X)-[Ru(X)2(CO)2(bpy)] (X = Cl, Br, I) byla použita k analýze reaktivity ekvatoriálního CO ligandu, koordinovaného v trans poloze k 2,2'-bipyridinovému ligandu (bpy), v excitovaném stavu. TD-DFT výpočty identifikovaly nejnižší elektronové přechody a singletní excitované stavy jako smíšené přechody přenosu náboje X-->bpy/Ru-->bpy ligand - ligand a kov - ligand (LLCT/MLCT). Pikosekundová časově rozlišená IR spektroskopie v oblasti ný(CO) vibrací ukázala, že CO disociace je sub-pikosekondová for X = Cl a Br, za vzniku penta koordinovaného intermediátu trans(X,X)-[Ru(X)2(CO)(bpy)]. Pro X = I, sub-pikosekundová CO disociace je pouze minoritním procesem.
Classification
Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Result continuities
Project
<a href="/en/project/1P04OCD14.20" target="_blank" >1P04OCD14.20: Oganometallic and Metallo-organic Building Blocks for Photonic Materials</a><br>
Continuities
Z - Vyzkumny zamer (s odkazem do CEZ)
Others
Publication year
2004
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
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Volume of the periodical
43
Issue of the periodical within the volume
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Country of publishing house
US - UNITED STATES
Number of pages
9
Pages from-to
7380-7388
UT code for WoS article
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EID of the result in the Scopus database
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