Structural, magnetic, redox and theoretical characterization of seven-coordinate first-row transition metal complexes with a macrocyclic ligand containing two benzimidazolyl N-pendant arms

Simple item page
dc.contributor.authorDrahoš, Bohuslavcs
dc.contributor.authorCísařová, Ivanacs
dc.contributor.authorLaguta, Oleksiics
dc.contributor.authorSantana, Vinicius Tadeucs
dc.contributor.authorNeugebauer, Petrcs
dc.contributor.authorHerchel, Radovancs
dc.coverage.issue14cs
dc.coverage.volume49cs
dc.date.issued2020-04-14cs
dc.description.abstractA 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.en
dc.formattextcs
dc.format.extent4425-4440cs
dc.format.mimetypeapplication/pdfcs
dc.identifier.citationDalton Transactions. 2020, vol. 49, issue 14, p. 4425-4440.en
dc.identifier.doi10.1039/d0dt00166jcs
dc.identifier.issn1477-9234cs
dc.identifier.orcid0000-0002-3567-414Xcs
dc.identifier.orcid0000-0002-2258-6140cs
dc.identifier.orcid0000-0001-7095-6401cs
dc.identifier.other163834cs
dc.identifier.researcheridF-4961-2019cs
dc.identifier.researcheridB-5381-2014cs
dc.identifier.researcheridI-7844-2013cs
dc.identifier.scopus54788236000cs
dc.identifier.urihttp://hdl.handle.net/11012/187017
dc.language.isoencs
dc.publisherRoyal Society of Chemistrycs
dc.relation.ispartofDalton Transactionscs
dc.relation.urihttps://pubs.rsc.org/en/content/articlelanding/2020/DT/D0DT00166J#!divAbstractcs
dc.rightsCreative Commons Attribution 4.0 Internationalcs
dc.rights.accessopenAccesscs
dc.rights.sherpahttp://www.sherpa.ac.uk/romeo/issn/1477-9234/cs
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/cs
dc.subjectSINGLE-ION-MAGNETen
dc.subjectSTATE PERTURBATION-THEORYen
dc.subjectBASIS-SETSen
dc.subjectCHAIN MAGNETen
dc.subjectANISOTROPYen
dc.subjectVALENCEen
dc.subjectRELAXATIONen
dc.subjectBEHAVIORen
dc.subjectIMPLEMENTATIONen
dc.subjectVISUALIZATIONen
dc.titleStructural, magnetic, redox and theoretical characterization of seven-coordinate first-row transition metal complexes with a macrocyclic ligand containing two benzimidazolyl N-pendant armsen
dc.type.driverarticleen
dc.type.statusPeer-revieweden
dc.type.versionpublishedVersionen
sync.item.dbidVAV-163834en
sync.item.dbtypeVAVen
sync.item.insts2025.02.03 15:50:48en
sync.item.modts2025.01.17 19:35:03en
thesis.grantorVysoké učení technické v Brně. Středoevropský technologický institut VUT. Magneto-Optická a THz Spektroskopiecs
Files
Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
d0dt00166j.pdf
Size:
3.89 MB
Format:
Adobe Portable Document Format
Description:
d0dt00166j.pdf
Download
Collections
Magneto-Optická a THz Spektroskopie