Entrapment of a Pseudo-Tetrahedral Co-II Center by Thioether Sulfur Bound {Co-2(mu-L)} Fragments: Synthesis, Field-Induced Single-Ion Magnetism and Catechol Oxidase Mimicking Activity

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F19%3A73596424" target="_blank" >RIV/61989592:15310/19:73596424 - isvavai.cz</a>

Výsledek na webu

<a href="https://onlinelibrary.wiley.com/doi/full/10.1002/asia.201901109" target="_blank" >https://onlinelibrary.wiley.com/doi/full/10.1002/asia.201901109</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/asia.201901109" target="_blank" >10.1002/asia.201901109</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Entrapment of a Pseudo-Tetrahedral Co-II Center by Thioether Sulfur Bound {Co-2(mu-L)} Fragments: Synthesis, Field-Induced Single-Ion Magnetism and Catechol Oxidase Mimicking Activity

Popis výsledku v původním jazyce

Simultaneous incorporation of both Co-II and Co-III ions within a new thioether S-bearing phenol-based ligand system, H3L (2,6-bis-[{2-(2-hydroxyethylthio)ethylimino}methyl]-4-methylphenol) formed [Co-5] aggregates [(CoCo4L2)-Co-II-L-III(mu-OH)(2)(mu(1,3)-O2CCH3)(2)](ClO4)(4) H2O (1) and [(CoCo4L2)-Co-II-L-III(mu-OH)(2)(mu(1,3)-O2CC2H5)(2)](ClO4)(4)H2O (2). The magnetic studies revealed axial zero-field splitting (ZFS) parameter, D/hc=-23.6 and -24.3 cm(-1), and E/D=0.03 and 0.00, respectively for 1 and 2. Dynamic magnetic data confirmed the complexes as SIMs with U-eff/k(B)=30 K (1) and 33 K (2), and tau(0)=9.1x10(-8) s (1), and 4.3x10(-8) s (2). The larger atomic radius of S compared to N gave rise to less variation in the distortion of tetrahedral geometry around central Co-II centers, thus affecting the D and U-eff/k(B) values. Theoretical studies also support the experimental findings and reveal the origin of the anisotropy parameters. In solutions, both 1 and 2 which produce {Co-2(III)(mu-L)} units, display solvent-dependent catechol oxidation behavior toward 3,5-di-tert-butylcatechol in air. The presence of an adjacent Co-III ion tends to assist the electron transfer from the substrate to the metal ion center, enhancing the catalytic oxidation rate.

Název v anglickém jazyce

Entrapment of a Pseudo-Tetrahedral Co-II Center by Thioether Sulfur Bound {Co-2(mu-L)} Fragments: Synthesis, Field-Induced Single-Ion Magnetism and Catechol Oxidase Mimicking Activity

Popis výsledku anglicky

Simultaneous incorporation of both Co-II and Co-III ions within a new thioether S-bearing phenol-based ligand system, H3L (2,6-bis-[{2-(2-hydroxyethylthio)ethylimino}methyl]-4-methylphenol) formed [Co-5] aggregates [(CoCo4L2)-Co-II-L-III(mu-OH)(2)(mu(1,3)-O2CCH3)(2)](ClO4)(4) H2O (1) and [(CoCo4L2)-Co-II-L-III(mu-OH)(2)(mu(1,3)-O2CC2H5)(2)](ClO4)(4)H2O (2). The magnetic studies revealed axial zero-field splitting (ZFS) parameter, D/hc=-23.6 and -24.3 cm(-1), and E/D=0.03 and 0.00, respectively for 1 and 2. Dynamic magnetic data confirmed the complexes as SIMs with U-eff/k(B)=30 K (1) and 33 K (2), and tau(0)=9.1x10(-8) s (1), and 4.3x10(-8) s (2). The larger atomic radius of S compared to N gave rise to less variation in the distortion of tetrahedral geometry around central Co-II centers, thus affecting the D and U-eff/k(B) values. Theoretical studies also support the experimental findings and reveal the origin of the anisotropy parameters. In solutions, both 1 and 2 which produce {Co-2(III)(mu-L)} units, display solvent-dependent catechol oxidation behavior toward 3,5-di-tert-butylcatechol in air. The presence of an adjacent Co-III ion tends to assist the electron transfer from the substrate to the metal ion center, enhancing the catalytic oxidation rate.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/LO1305" target="_blank" >LO1305: Rozvoj centra pokročilých technologií a materiálů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

Chemistry-An Asian Journal

ISSN

1861-4728

e-ISSN

—

Svazek periodika

14

Číslo periodika v rámci svazku

21

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

17

Strana od-do

3898-3914

Kód UT WoS článku

000495080600019

EID výsledku v databázi Scopus

2-s2.0-85074364888