Perfluorinated porphyrazines. 3. Synthesis, spectral-luminescence and electrochemical properties of perfluorinated octaphenylporphyrazinatozinc (II)

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Perfluorinated porphyrazines. 3. Synthesis, spectral-luminescence and electrochemical properties of perfluorinated octaphenylporphyrazinatozinc (II)

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Perfluorinated porphyrazines. 3. Synthesis, spectral-luminescence and electrochemical properties of perfluorinated octaphenylporphyrazinatozinc (II)

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Journal of Fluorine Chemistry

ISSN

0022-1139

e-ISSN

—

Svazek periodika

214

Číslo periodika v rámci svazku

October

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

8

Strana od-do

86-93

Kód UT WoS článku

000446808600013

EID výsledku v databázi Scopus

2-s2.0-85051799005