Iron(II), Cobalt(II), and Nickel(II) Complexes of Bis(sulfonamido)benzenes: Redox Properties, Large Zero-Field Splittings, and Single-Ion Magnets
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26620%2F21%3APU140755" target="_blank" >RIV/00216305:26620/21:PU140755 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02949" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02949</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.0c02949" target="_blank" >10.1021/acs.inorgchem.0c02949</a>
Alternative languages
Result language
angličtina
Original language name
Iron(II), Cobalt(II), and Nickel(II) Complexes of Bis(sulfonamido)benzenes: Redox Properties, Large Zero-Field Splittings, and Single-Ion Magnets
Original language description
Metal complexes of 1,2-diamidobenzenes have been long studied because of their intriguing redox properties and electronic structures. We present here a series of such complexes with 1,2-bis(sulfonamido)benzene ligands to probe the utility of these ligands for generating a large zero-field splitting (ZFS, D) in metal complexes that possibly act as single-ion magnets. To this end, we have synthesized a series of homoleptic ate complexes of the form (X)(n)[M{bis(sulfonamido)benzene}(2)] (n equals 4 minus the oxidation state of the metal), where M (Fe/Co/NO, X [K+/(K-18-c-6)(+)/(HNEt3)(+), with 18-c-6 = 18 crown ether 6], and the substituents (methyl and tolyl) on the ligand [bmsab = 1,2-bis(methanesulfonamido)benzene; btsab = 1,2-bis(toluenesulfonamido)benzene] were varied to analyze their effect on the ZFS, possible single-ion-magnet properties, and redox behavior of these metal complexes. A combination of X-ray crystallography, (spectro)electrochemistry, superconducting quantum interference device magnetometry, high-frequency electron paramagnetic resonance spectroscopy, and Mossbauer spectroscopy was used to investigate the electronic/geometric structures of these complexes and the aforementioned properties. These investigations show that the cobalt(II) complexes display very high negative D values in the range of -100 to -130 cm(-1), and the nickel(II) complexes display very high positive D values of 76 and 58 cm(-1). In addition, the cobalt(II) complexes shows barriers of 200-260 cm(-1) and slow relaxation of the magnetization in the absence of an external magnetic field, underscoring the robustness of this class of complexes. The iron(II) complex exhibits a D value of -3.29 cm(-1) and can be chemically oxidized to an iron(III) complex that has D = -1.96 cm(-1). These findings clearly show that bis(sulfonamido)benzenes are ideally suited to stabilize ate complexes, to generate very high ZFSs at the metal centers with single-ion-magnet properties, and to induce exc
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
2021
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
1520-510X
Volume of the periodical
60
Issue of the periodical within the volume
5
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
2953-2963
UT code for WoS article
000625446000014
EID of the result in the Scopus database
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