Pentagonal Bipyramidal First-Row Transition Metal Complexes with Macrocyclic Ligand Containing Two Pyridine-N-Oxide Pendant Arms: Structural, Magnetic, and Theoretical Studies

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F25%3A73633989" target="_blank" >RIV/61989592:15310/25:73633989 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5c03514" target="_blank" >https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5c03514</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.5c03514" target="_blank" >10.1021/acs.inorgchem.5c03514</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Pentagonal Bipyramidal First-Row Transition Metal Complexes with Macrocyclic Ligand Containing Two Pyridine-N-Oxide Pendant Arms: Structural, Magnetic, and Theoretical Studies

Popis výsledku v původním jazyce

A heptadentate 15-membered pyridine-based macrocyclic ligand containing two pyridine-N-oxide pendant arms (L4 = 3,12-bis((pyridine-1-oxide-2-yl)methyl)-6,9-dioxa-3,12,18-triazabicyclo[12.3.1]octadeca-1(18),14,16-triene) was synthesized together with its first-row transition metal complexes with the general formula [M(L4)](ClO4)2&lt;middle dot&gt;1DMF (MII = Mn (1), Fe (2), Co (3), and Ni (4); DMF = N,N&apos;-dimethylformamide), which were thoroughly investigated. According to the obtained X-ray crystal structures, all complexes possess axially compressed pentagonal bipyramidal geometry with a coordination number of 7 for 1-3 or 5 + 2 for Ni(II) complex 4 with a large Jahn-Teller distortion. Fe(II), Co(II), and Ni(II) complexes 2, 3, and 4 show pronounced magnetic anisotropy (D = 4.47, 30.10, -7.58 cm-1, respectively). The magnetic properties of the studied complexes were supported by theoretical calculations, which corresponded very well to the experimental data for magnetic anisotropy. Furthermore, complex 3 showed a field-induced single-molecule magnet behavior described best by the combination of direct (DHm = 145 K-1s-1) and Raman (C = 0.58 K-ns-1 for n = 5.76) relaxation processes. Magneto-structural correlation for Fe(II)/Co(II)/Ni(II) complexes with L4 and previously studied structurally similar ligands revealed a significant impact of the coordination ability of the functional group in pendant arms on the final magnetic anisotropy (pi-acceptors appear to be more suitable).

Název v anglickém jazyce

Pentagonal Bipyramidal First-Row Transition Metal Complexes with Macrocyclic Ligand Containing Two Pyridine-N-Oxide Pendant Arms: Structural, Magnetic, and Theoretical Studies

Popis výsledku anglicky

A heptadentate 15-membered pyridine-based macrocyclic ligand containing two pyridine-N-oxide pendant arms (L4 = 3,12-bis((pyridine-1-oxide-2-yl)methyl)-6,9-dioxa-3,12,18-triazabicyclo[12.3.1]octadeca-1(18),14,16-triene) was synthesized together with its first-row transition metal complexes with the general formula [M(L4)](ClO4)2&lt;middle dot&gt;1DMF (MII = Mn (1), Fe (2), Co (3), and Ni (4); DMF = N,N&apos;-dimethylformamide), which were thoroughly investigated. According to the obtained X-ray crystal structures, all complexes possess axially compressed pentagonal bipyramidal geometry with a coordination number of 7 for 1-3 or 5 + 2 for Ni(II) complex 4 with a large Jahn-Teller distortion. Fe(II), Co(II), and Ni(II) complexes 2, 3, and 4 show pronounced magnetic anisotropy (D = 4.47, 30.10, -7.58 cm-1, respectively). The magnetic properties of the studied complexes were supported by theoretical calculations, which corresponded very well to the experimental data for magnetic anisotropy. Furthermore, complex 3 showed a field-induced single-molecule magnet behavior described best by the combination of direct (DHm = 145 K-1s-1) and Raman (C = 0.58 K-ns-1 for n = 5.76) relaxation processes. Magneto-structural correlation for Fe(II)/Co(II)/Ni(II) complexes with L4 and previously studied structurally similar ligands revealed a significant impact of the coordination ability of the functional group in pendant arms on the final magnetic anisotropy (pi-acceptors appear to be more suitable).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

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

1520-510X

Svazek periodika

64

Číslo periodika v rámci svazku

46

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

15

Strana od-do

22683-22697

Kód UT WoS článku

001611278100001

EID výsledku v databázi Scopus

2-s2.0-105022733625