Reversible Spin-State Switching and Tuning of Nuclearity and Dimensionality via Nonlinear Pseudohalides in Cobalt(II) Complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F20%3A73604070" target="_blank" >RIV/61989592:15310/20:73604070 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02887" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02887</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.0c02887" target="_blank" >10.1021/acs.inorgchem.0c02887</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Reversible Spin-State Switching and Tuning of Nuclearity and Dimensionality via Nonlinear Pseudohalides in Cobalt(II) Complexes

Popis výsledku v původním jazyce

The self-assembly of a macrocyclic tetradentate ligand, cobalt(II) tetrafluoroborate, and nonlinear pseudohalides (dicyanamide and tricyanomethanide) has led to two cobalt(11) complexes, {[Co(L)(mu(1,5)-dca)](BF4)center dot MeOH}(n) (1) and [Co-2(L)(2) (mu(1,5)-tcm)(2)](BF4)(2) (2) (L = N,N&apos;-di-tert-butyl-2,11-diaza[3,3](2,6)pyridinophane; dca(-) = dicyanamido; tcmtricyanomethanido). Both complexes were characterized by single-crystal X-ray diffraction, spectroscopic, magnetic, and electrochemical studies. Structural analyses revealed that 1 displays a one-dimensional (1D) coordination polymer containing [Co-(L)](2+) repeating units bridged by mu(1,5)-dicyanamido groups in cis positions, while 2 represents a discreate dinuclear cobalt(II) molecule bridged by two mu(1,5)-tricyanomethanido groups in a cis conformation. Both complexes have a CoN6 coordination environment around each cobalt center offered by the tetradentate ligand and cis coordinating bridging ligands. Complex 1 exhibits a high-spin (S = 3/2) state of cobalt(II) in the temperature range of 2-300 K with a weak ferromagnetic coupling between two dicyanamido-bridged cobalt(II) centers. Interestingly, complex 2 exhibits reversible spin-state switching associated with spin-spin coupling. Complexes 1 and 2 also exhibit interesting redox-stimuli-based reversible paramagnetic high-spin cobalt(II) to diamagnetic low-spin cobalt(III) conversion, offering an additional way to switch magnetic properties. A detailed theoretical calculation was consistent with the stated results.

Název v anglickém jazyce

Reversible Spin-State Switching and Tuning of Nuclearity and Dimensionality via Nonlinear Pseudohalides in Cobalt(II) Complexes

Popis výsledku anglicky

The self-assembly of a macrocyclic tetradentate ligand, cobalt(II) tetrafluoroborate, and nonlinear pseudohalides (dicyanamide and tricyanomethanide) has led to two cobalt(11) complexes, {[Co(L)(mu(1,5)-dca)](BF4)center dot MeOH}(n) (1) and [Co-2(L)(2) (mu(1,5)-tcm)(2)](BF4)(2) (2) (L = N,N&apos;-di-tert-butyl-2,11-diaza[3,3](2,6)pyridinophane; dca(-) = dicyanamido; tcmtricyanomethanido). Both complexes were characterized by single-crystal X-ray diffraction, spectroscopic, magnetic, and electrochemical studies. Structural analyses revealed that 1 displays a one-dimensional (1D) coordination polymer containing [Co-(L)](2+) repeating units bridged by mu(1,5)-dicyanamido groups in cis positions, while 2 represents a discreate dinuclear cobalt(II) molecule bridged by two mu(1,5)-tricyanomethanido groups in a cis conformation. Both complexes have a CoN6 coordination environment around each cobalt center offered by the tetradentate ligand and cis coordinating bridging ligands. Complex 1 exhibits a high-spin (S = 3/2) state of cobalt(II) in the temperature range of 2-300 K with a weak ferromagnetic coupling between two dicyanamido-bridged cobalt(II) centers. Interestingly, complex 2 exhibits reversible spin-state switching associated with spin-spin coupling. Complexes 1 and 2 also exhibit interesting redox-stimuli-based reversible paramagnetic high-spin cobalt(II) to diamagnetic low-spin cobalt(III) conversion, offering an additional way to switch magnetic properties. A detailed theoretical calculation was consistent with the stated results.

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

2020

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

—

Svazek periodika

59

Číslo periodika v rámci svazku

23

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

17638-17649

Kód UT WoS článku

000599190300094

EID výsledku v databázi Scopus

2-s2.0-85096537125