Reversible Spin-State Switching and Tuning of Nuclearity and Dimensionality via Nonlinear Pseudohalides in Cobalt(II) Complexes
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Reversible Spin-State Switching and Tuning of Nuclearity and Dimensionality via Nonlinear Pseudohalides in Cobalt(II) Complexes
Original language description
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'-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.
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
2020
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
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Volume of the periodical
59
Issue of the periodical within the volume
23
Country of publishing house
US - UNITED STATES
Number of pages
12
Pages from-to
17638-17649
UT code for WoS article
000599190300094
EID of the result in the Scopus database
2-s2.0-85096537125