Impact of counter anions on spin-state switching of manganese(III) complexes containing an azobenzene ligand

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F22%3A73615172" target="_blank" >RIV/61989592:15310/22:73615172 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlehtml/2022/dt/d2dt00660j" target="_blank" >https://pubs.rsc.org/en/content/articlehtml/2022/dt/d2dt00660j</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d2dt00660j" target="_blank" >10.1039/d2dt00660j</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Impact of counter anions on spin-state switching of manganese(III) complexes containing an azobenzene ligand

Popis výsledku v původním jazyce

Four mononuclear manganese(III) complexes coordinated with photo-active hexadentate azobenzene ligands, (Mn(5azo-sal(2)-323)](X) (X = Cl, 1; X = BF4, 2; X = ClO4, 3; X = PF6, 4), were prepared. The impact of various counter anions on the stabilization and switching of the spin state of the manganese(m) center was explored through detailed magneto-structural investigation using variable temperature single-crystal X-ray diffraction, magnetic, spectroscopic, and spectroelectrochemical studies, along with theoretical calculations. All four complexes consisted of an isostructural monocationic distorted octahedral MnN4O2 coordination environment offered by the hexadentate ligand and Cl-, BF4-, ClO4-, and PF6- as counter anions respectively. Complex 1 with a spherical Cl- counter anion showed a reversible and gradual spinstate switching between low-spin (LS) (S = 1) and high-spin (HS) (S = 2) states above 400 K, where non-covalent cation-anion interactions played a significant role in stabilizing the LS state. While, irrespective of the shape of the counter anion, complexes 2-4 remained in the HS state throughout the measured temperature range of 300-2 K, where strong pi-pi interaction between the azobenzene motifs among cationic units played a substantial role in stabilizing the HS state. Furthermore, magnetic data analyses revealed significantly large zero-field splitting in the S = 1 state for 1 (D = 19.4 cm(-1), E/D = 0.008) in comparison with that in the S = 2 state for 2-4 (D = 3.99-4.97 cm(-1), E/D = 0.002-0.195). Spectroelectrochemical investigations revealed the quasi-reversible reduction and oxidation of the manganese(III) center to manganese(II) and manganese(IV), respectively. A detailed theoretical calculation at the DFT and CASSCF level of theory was carried out to better understand the magneto-structural correlation.

Název v anglickém jazyce

Impact of counter anions on spin-state switching of manganese(III) complexes containing an azobenzene ligand

Popis výsledku anglicky

Four mononuclear manganese(III) complexes coordinated with photo-active hexadentate azobenzene ligands, (Mn(5azo-sal(2)-323)](X) (X = Cl, 1; X = BF4, 2; X = ClO4, 3; X = PF6, 4), were prepared. The impact of various counter anions on the stabilization and switching of the spin state of the manganese(m) center was explored through detailed magneto-structural investigation using variable temperature single-crystal X-ray diffraction, magnetic, spectroscopic, and spectroelectrochemical studies, along with theoretical calculations. All four complexes consisted of an isostructural monocationic distorted octahedral MnN4O2 coordination environment offered by the hexadentate ligand and Cl-, BF4-, ClO4-, and PF6- as counter anions respectively. Complex 1 with a spherical Cl- counter anion showed a reversible and gradual spinstate switching between low-spin (LS) (S = 1) and high-spin (HS) (S = 2) states above 400 K, where non-covalent cation-anion interactions played a significant role in stabilizing the LS state. While, irrespective of the shape of the counter anion, complexes 2-4 remained in the HS state throughout the measured temperature range of 300-2 K, where strong pi-pi interaction between the azobenzene motifs among cationic units played a substantial role in stabilizing the HS state. Furthermore, magnetic data analyses revealed significantly large zero-field splitting in the S = 1 state for 1 (D = 19.4 cm(-1), E/D = 0.008) in comparison with that in the S = 2 state for 2-4 (D = 3.99-4.97 cm(-1), E/D = 0.002-0.195). Spectroelectrochemical investigations revealed the quasi-reversible reduction and oxidation of the manganese(III) center to manganese(II) and manganese(IV), respectively. A detailed theoretical calculation at the DFT and CASSCF level of theory was carried out to better understand the magneto-structural correlation.

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

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

51

Číslo periodika v rámci svazku

19

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

7681-7694

Kód UT WoS článku

000791978300001

EID výsledku v databázi Scopus

2-s2.0-85130631648