Electronic structure and excited states of rhenium(I) amido and phosphido carbonyl-bipyridine complexes studied by picosecond time-resolved IR spectroscopy and DFT calculations
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F06%3A00049090" target="_blank" >RIV/61388955:_____/06:00049090 - 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
Electronic structure and excited states of rhenium(I) amido and phosphido carbonyl-bipyridine complexes studied by picosecond time-resolved IR spectroscopy and DFT calculations
Original language description
UV-vis absorption and picosecond time-resolved IR (TRIR) spectra of amido and phosphido complexes fac-[Re-(ER2)(CO)(3)(bpy)] (ER2 = NHPh, NTol(2), PPh2, bpy = 2,2´-bipyridine, Tol = 4-methylphenyl) were investigated in conjunction with DFT and TD-DFT calculations in order to understand their ground-state electronic structure, low-lying electronic transitions and excited-state character and dynamics. The HOMO is localized at the amido/phosphido ligand. Amide and phosphide ligands are sigma-bonded to Re,the .pi. interaction being negligible. Absorption spectra show a weak band at low energies (1.7-2.1 eV) that arises from essentially pure ER2 -> bpy ligand-to-ligand charge transfer (LLCT). The lowest excited state is the corresponding triplet, (LLCT)-L-3. Low triplet energies and large distortions diminish the excited-state lifetimes to 85 and 270 ps for NHPh and NTol(2), respectively, and to ca. 30 ps for PPh2.
Czech name
Elektronová struktura a excitované stavu rhenium(I) amidových a fosfidových karbonyl - bipyridin komplexů studované pikosekundovou IR spektroskopií a DFT výpočty
Czech description
UV-vis absorpční a pikosekundová časově rozlišená IR (TRIR) spektra amidových a fosfidových komplexů fac-[Re(ER2)(CO)3(bpy)] (ER2 = NHPh, NTol2, PPh2, bpy = 2,2?-bipyridin, Tol = 4-methylfenyl) byla zkoumána v současně s DFT a TD-DFT výpočty, aby bylo možno objasnit jejich elektronovou strukturu základního stavu, nízko ležící elektronové přechody a charakter excitovaných stavů a jejich dynamiku. Amidové a fosfidové ligandy jsou vázány .sigma.- vazbou k Re, .pi.-interakce je zanedbatelná. Absorpční spektra se vyznačují slabými pásy při nízkých energiích (1.7 ? 2.1 eV) tvořenými převážně excitacemi přenosu náboje ER2--> bpy ligand - ligand (LLCT).
Classification
Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CG - Electrochemistry
OECD FORD branch
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Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
Z - Vyzkumny zamer (s odkazem do CEZ)
Others
Publication year
2006
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
45
Issue of the periodical within the volume
24
Country of publishing house
US - UNITED STATES
Number of pages
9
Pages from-to
9789-9797
UT code for WoS article
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EID of the result in the Scopus database
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