Perfluorinated porphyrazines. 3. Synthesis, spectral-luminescence and electrochemical properties of perfluorinated octaphenylporphyrazinatozinc (II)
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11160%2F18%3A10382763" target="_blank" >RIV/00216208:11160/18:10382763 - isvavai.cz</a>
Result on the web
<a href="http://www.sciencedirect.com/science/article/pii/S0022113918302094" target="_blank" >http://www.sciencedirect.com/science/article/pii/S0022113918302094</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1016/j.jfluchem.2018.08.006" target="_blank" >10.1016/j.jfluchem.2018.08.006</a>
Alternative languages
Result language
angličtina
Original language name
Perfluorinated porphyrazines. 3. Synthesis, spectral-luminescence and electrochemical properties of perfluorinated octaphenylporphyrazinatozinc (II)
Original language description
Octakis(pentafluorophenyl)porphyrazinatozinc(II), [ZnPAF(40)], has been prepared by template cyclotetramerization of perfluorinated alpha,beta-dicyanostylbene in the presence of ZnCl2 in a melt. Influence of perfluorination of phenyl rings on spectral, electrochemical and acid-base properties of porphyrazine macrocycle is revealed by comparison with octaphenylporphyrazinatozinc(II), [ZnPA], which was prepared similarly from trans-alpha,beta-dicyanostylbene. B3LYP DFT calculations show that perfluorination of phenyl rings stabilizes the frontier molecular orbitals of the porphyrazine macrocycle and slightly increases the HOMO-LUMO gap. As a result the reduction of the macrocycle is strongly facilitated and observed for [ZnPAF(40)] at 0.26 V vs Ag/AgCl, by 0.56 V in the less negative region as compared to [ZnPA]. Perfluorination leads to hypsochromic shift of the Q-band (lowest pi pi* transition) in the electronic absorption spectra from 633 nm for [ZnPA] to 623 nm for [ZnPAF(40)] and increases the fluorescence quantum yield Phi(F) from 0.12 to 0.19, respectively (values in THF). [ZnPAF(40)] has higher efficiency in generation of singlet oxygen (Phi(Delta) = 0.60) than [ZnPA] (Phi(Delta) = 0.37) (in THF). Introduction of 40 fluorine atoms decreases the basicity of the porphyrazine macrocycle almost by 3 orders of magnitude according to spectrophotometric titration study in CH2Cl2-CF3COOH medium.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10401 - Organic chemistry
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Fluorine Chemistry
ISSN
0022-1139
e-ISSN
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Volume of the periodical
214
Issue of the periodical within the volume
October
Country of publishing house
CH - SWITZERLAND
Number of pages
8
Pages from-to
86-93
UT code for WoS article
000446808600013
EID of the result in the Scopus database
2-s2.0-85051799005