Effect of Ligand Chain Length for Tuning of Molecular Dimensionality and Magnetic Relaxation in Redox Active Cobalt(II) EDOT Complexes (EDOT=3,4-Ethylenedioxythiophene)

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F22%3A73615192" target="_blank" >RIV/61989592:15310/22:73615192 - isvavai.cz</a>

Výsledek na webu

<a href="https://onlinelibrary.wiley.com/doi/epdf/10.1002/asia.202200404" target="_blank" >https://onlinelibrary.wiley.com/doi/epdf/10.1002/asia.202200404</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/asia.202200404" target="_blank" >10.1002/asia.202200404</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Effect of Ligand Chain Length for Tuning of Molecular Dimensionality and Magnetic Relaxation in Redox Active Cobalt(II) EDOT Complexes (EDOT=3,4-Ethylenedioxythiophene)

Popis výsledku v původním jazyce

Four cobalt(II) complexes, [Co(L1)(2)(NCX)(2)(MeOH)(2)] (X=S (1), Se (2)) and {[Co(L2)(2)(NCX)(2)]}n (X=S (3), Se (4)) (L1=2,5-dipyridyl-3,4,-ethylenedioxylthiophene and L2=2,5-diethynylpyridinyl-3,4-ethylenedioxythiophene), were synthesized by incorporating ethylenedioxythiophene based redox-active luminescence ligands. All these complexes have been well characterized using single-crystal X-ray diffraction analyses, spectroscopic and magnetic investigations. Magneto-structural studies showed that 1 and 2 adopt a mononuclear structure with CoN4O2 octahedral coordination geometry while 3 and 4 have a 2D [4x4] rhombic grid coordination networks (CNs) where each cobalt(II) center is in a CoN6 octahedral coordination environment. Static magnetic measurements reveal that all four complexes displayed a high spin (HS) (S=3/2) state between 2 and 280 K which was further confirmed by X-band and Q-band EPR studies. Remarkably, along with the molecular dimensionality (0D and 2D) the modification in the axial coligands lead to a significant difference in the dynamic magnetic properties of the monomers and CNs at low temperatures. All complexes display slow magnetic relaxation behavior under an external dc magnetic field. For the complexes with NCS- as coligand observed higher energy barrier for spin reversal in comparison to the complexes with NCSe- as coligand, while mononuclear complex 1 exhibited a higher energy barrier than that of CN 3. Theoretical calculations at the DFT and CASSCF level of theory have been performed to get more insight into the electronic structure and magnetic properties of all four complexes.

Název v anglickém jazyce

Effect of Ligand Chain Length for Tuning of Molecular Dimensionality and Magnetic Relaxation in Redox Active Cobalt(II) EDOT Complexes (EDOT=3,4-Ethylenedioxythiophene)

Popis výsledku anglicky

Four cobalt(II) complexes, [Co(L1)(2)(NCX)(2)(MeOH)(2)] (X=S (1), Se (2)) and {[Co(L2)(2)(NCX)(2)]}n (X=S (3), Se (4)) (L1=2,5-dipyridyl-3,4,-ethylenedioxylthiophene and L2=2,5-diethynylpyridinyl-3,4-ethylenedioxythiophene), were synthesized by incorporating ethylenedioxythiophene based redox-active luminescence ligands. All these complexes have been well characterized using single-crystal X-ray diffraction analyses, spectroscopic and magnetic investigations. Magneto-structural studies showed that 1 and 2 adopt a mononuclear structure with CoN4O2 octahedral coordination geometry while 3 and 4 have a 2D [4x4] rhombic grid coordination networks (CNs) where each cobalt(II) center is in a CoN6 octahedral coordination environment. Static magnetic measurements reveal that all four complexes displayed a high spin (HS) (S=3/2) state between 2 and 280 K which was further confirmed by X-band and Q-band EPR studies. Remarkably, along with the molecular dimensionality (0D and 2D) the modification in the axial coligands lead to a significant difference in the dynamic magnetic properties of the monomers and CNs at low temperatures. All complexes display slow magnetic relaxation behavior under an external dc magnetic field. For the complexes with NCS- as coligand observed higher energy barrier for spin reversal in comparison to the complexes with NCSe- as coligand, while mononuclear complex 1 exhibited a higher energy barrier than that of CN 3. Theoretical calculations at the DFT and CASSCF level of theory have been performed to get more insight into the electronic structure and magnetic properties of all four complexes.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

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

1861-471X

Svazek periodika

17

Číslo periodika v rámci svazku

16

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

12

Strana od-do

"e202200404-1"-"e202200404-12"

Kód UT WoS článku

000811250100001

EID výsledku v databázi Scopus

2-s2.0-85131862044