Impact of counter anions on spin-state switching of manganese(III) complexes containing an azobenzene ligand
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Impact of counter anions on spin-state switching of manganese(III) complexes containing an azobenzene ligand
Original language description
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.
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
10402 - Inorganic and nuclear chemistry
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2022
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
1477-9234
Volume of the periodical
51
Issue of the periodical within the volume
19
Country of publishing house
GB - UNITED KINGDOM
Number of pages
14
Pages from-to
7681-7694
UT code for WoS article
000791978300001
EID of the result in the Scopus database
2-s2.0-85130631648