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DRAHOŠ, B. CÍSAŘOVÁ, I. LAGUTA, O. SANTANA, V. NEUGEBAUER, P. HERCHEL, R.
Originální název
Structural, magnetic, redox and theoretical characterization of seven-coordinate first-row transition metal complexes with a macrocyclic ligand containing two benzimidazolyl N-pendant arms
Typ
článek v časopise ve Web of Science, Jimp
Jazyk
angličtina
Originální abstrakt
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.
Klíčová slova
SINGLE-ION-MAGNET; STATE PERTURBATION-THEORY; BASIS-SETS; CHAIN MAGNET; ANISOTROPY; VALENCE; RELAXATION; BEHAVIOR; IMPLEMENTATION; VISUALIZATION
Autoři
DRAHOŠ, B.; CÍSAŘOVÁ, I.; LAGUTA, O.; SANTANA, V.; NEUGEBAUER, P.; HERCHEL, R.
Vydáno
14. 4. 2020
Nakladatel
Royal Society of Chemistry
Místo
CAMBRIDGE
ISSN
1477-9234
Periodikum
Dalton Transactions
Ročník
49
Číslo
14
Stát
Spojené království Velké Británie a Severního Irska
Strany od
4425
Strany do
4440
Strany počet
16
URL
https://pubs.rsc.org/en/content/articlelanding/2020/DT/D0DT00166J#!divAbstract
Plný text v Digitální knihovně
http://hdl.handle.net/11012/187017
BibTex
@article{BUT163834, author="Bohuslav {Drahoš} and Ivana {Císařová} and Oleksii {Laguta} and Vinicius Tadeu {Santana} and Petr {Neugebauer} and Radovan {Herchel}", title="Structural, magnetic, redox and theoretical characterization of seven-coordinate first-row transition metal complexes with a macrocyclic ligand containing two benzimidazolyl N-pendant arms", journal="Dalton Transactions", year="2020", volume="49", number="14", pages="4425--4440", doi="10.1039/d0dt00166j", issn="1477-9234", url="https://pubs.rsc.org/en/content/articlelanding/2020/DT/D0DT00166J#!divAbstract" }