Metal-Induced Tautomerization of p- to o-Quinone Compounds: Experimental Evidence from CuI and ReI Complexes of Azophenine and DFT Studies
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F04%3A00101025" target="_blank" >RIV/61388955:_____/04:00101025 - 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
Metal-Induced Tautomerization of p- to o-Quinone Compounds: Experimental Evidence from CuI and ReI Complexes of Azophenine and DFT Studies
Original language description
Azophenine (7,8-diphenyl-2,5-bis(phenylamino)-p-quinonediimine, Lp) reacts with [Cu(PPh3)4](BF4) or Re(CO)5Cl to yield the (Ph3P)2Cu+ or (OC)3ClRe complex of the tautomeric form 7,8-diphenyl-4,5-bis(phenylamino)-o-quinonediimine, Lo, as evident from structure determinations and from very intense metal-to-ligand charge transfer (MLCT) transitions in the visible region. Time-dependent DFT (TD-DFT) calculations on model complexes (NN)Re(CO)3Cl confirm the spectroscopic results, showing considerably higheroscillator strengths of the MLCT transition for the o-quinonediimine complexes in comparison to compounds with NN = 1,4-dialkyl-1,4-diazabutadiene. The cationic copper(I) complex is additionally stabilized through hydrogen bonding between two now ortho-positioned NHPh substituents and one fluoride of the BF4- anion. DFT Calculations on the model ligands p-quinonediimine or 2,5-diamino-p-quinonediimine and their ortho-quinonoid forms with and without Li+ or Cu+.
Czech name
Kovem ? indukovaná para - orto tautomerizace chinonových sloučenin: experimentální a DFT studie Cu(I) a Re(I) komplexů azopheninu
Czech description
Azophenin (7,8-diphenyl-2,5-bis(phenylamino)-p-quinonediimin, Lp) reaguje s [Cu(PPh3)4](BF4) nebo Re(CO)5Cl za vzniku (Ph3P)2Cu+ nebo (OC)3ClRe komplexů tautomerické formy 7,8-diphenyl-4,5-bis(phenylamino)-o-quinonediiminu, Lo, jak vyplývá z určené struktury a velmi intensivních přechodů přenosu náboje kov - ligand (MLCT) ve viditelné oblasti spektra. Výpočty pomocí časově závislé DFT metody (TD-DFT) pro komplex (N^N)Re(CO)3Cl potvrdily spektroskopické výsledky, a ukázaly na výrazně vyšší síly oscilátoru pro MLCT přechody o-quinonediiminových komplexů ve srovnání s N^N = 1,4-dialkyl-1,4-diazabutadienovými komplexy.
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/OC%20D14.20" target="_blank" >OC D14.20: 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
Chemistry European Journal
ISSN
0947-6539
e-ISSN
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Volume of the periodical
10
Issue of the periodical within the volume
1
Country of publishing house
DE - GERMANY
Number of pages
6
Pages from-to
149-154
UT code for WoS article
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EID of the result in the Scopus database
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