Structural, magnetic, redox and theoretical characterization of seven-coordinate first-row transition metal complexes with a macrocyclic ligand containing two benzimidazolyl N-pendant arms
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F20%3A73603247" target="_blank" >RIV/61989592:15310/20:73603247 - isvavai.cz</a>
Alternative codes found
RIV/00216208:11310/20:10410669 RIV/00216305:26620/20:PU136394
Result on the web
<a href="https://pubs.rsc.org/en/content/articlehtml/2020/dt/d0dt00166j" target="_blank" >https://pubs.rsc.org/en/content/articlehtml/2020/dt/d0dt00166j</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d0dt00166j" target="_blank" >10.1039/d0dt00166j</a>
Alternative languages
Result language
angličtina
Original language name
Structural, magnetic, redox and theoretical characterization of seven-coordinate first-row transition metal complexes with a macrocyclic ligand containing two benzimidazolyl N-pendant arms
Original language description
A structurally new heptadentate derivative of a 15-membered pyridine-based macrocycle containing two benzimidazol-2-yl-methyl N-pendant arms (L = 3,12-bis((1H-benzimidazol-2-yl)methyl)-6,9-dioxa-3,12,18-triazabicyclo[12.3.1]octadeca-1(18),14,16-triene) was synthesized and its complexes with the general formula [M(L)](ClO4)(2)center dot 1.5CH(3)NO(2) (M = Mn-II (1), Fe-II (2), Co-II (3) and Ni-II (4)) were thoroughly investigated. X-ray crystal structures confirmed that all complexes are seven-coordinate with axially compressed pentagonal bipyramidal geometry having the largest distortion for Ni-II complex 4. Fe-II, Co-II and Ni-II complexes 2, 3 and 4 show rather large magnetic anisotropy manifested by moderate to high obtained values of the axial zero-field splitting parameter D (7.9, 40.3, and -17.2 cm(-1), respectively). Magneto-structural correlation of the Fe-II, Co-II and Ni-II complexes with L and with previously studied structurally similar ligands revealed a significant impact of the functional group in pendant arms on the magnetic anisotropy especially that of the Co-II and Ni-II complexes and some recommendations concerning the ligand-field design important for anisotropy tuning in future. Furthermore, complex 3 showed field-induced single-molecule magnet behavior described with the Raman (C = 507 K-n s(-1) for n = 2.58) relaxation process. The magnetic properties of the studied complexes were supported by theoretical calculations, which very well correspond with the experimental data of magnetic anisotropy. Electrochemical measurements revealed high positive redox potentials for M3+/2+ couples and high negative redox potentials for M2+/+ couples, which indicate the stabilization of the oxidation state +II expected for the sigma-donor/pi-acceptor ability of benzimidazole functional groups.
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
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
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
Dalton Transactions
ISSN
1477-9226
e-ISSN
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Volume of the periodical
49
Issue of the periodical within the volume
14
Country of publishing house
GB - UNITED KINGDOM
Number of pages
16
Pages from-to
4425-4440
UT code for WoS article
000526110700024
EID of the result in the Scopus database
2-s2.0-85081614255