Iron(II), Cobalt(II), and Nickel(II) Complexes of Bis(sulfonamido)benzenes: Redox Properties, Large Zero-Field Splittings, and Single-Ion Magnets

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Iron(II), Cobalt(II), and Nickel(II) Complexes of Bis(sulfonamido)benzenes: Redox Properties, Large Zero-Field Splittings, and Single-Ion Magnets

Popis výsledku v původním jazyce

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

Název v anglickém jazyce

Iron(II), Cobalt(II), and Nickel(II) Complexes of Bis(sulfonamido)benzenes: Redox Properties, Large Zero-Field Splittings, and Single-Ion Magnets

Popis výsledku anglicky

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

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

2021

Kód důvěrnosti údajů

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

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

1520-510X

Svazek periodika

60

Číslo periodika v rámci svazku

5

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

2953-2963

Kód UT WoS článku

000625446000014

EID výsledku v databázi Scopus

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