Effective tuning of magnetic anisotropy in distorted pentagonal bipyramidal Ni(ii) complexes via substitution of axial coligands
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F22%3A73615231" target="_blank" >RIV/61989592:15310/22:73615231 - isvavai.cz</a>
Výsledek na webu
<a href="https://pubs.rsc.org/en/content/articlehtml/2022/dt/d2dt02867k" target="_blank" >https://pubs.rsc.org/en/content/articlehtml/2022/dt/d2dt02867k</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d2dt02867k" target="_blank" >10.1039/d2dt02867k</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Effective tuning of magnetic anisotropy in distorted pentagonal bipyramidal Ni(ii) complexes via substitution of axial coligands
Popis výsledku v původním jazyce
A series of Ni(ii) complexes with pyridine-based macrocyclic ligand L (3,12,18-triaza-6,9-dioxabicyclo[12.3.1]octadeca-1(18),14,16-triene) with general formula [Ni(L)(X)(2)](0/2+) (X = Br- (1), I- (2), CH3CN (3), NCS- (4), imidazole (5)) was prepared and thoroughly investigated. X-ray molecular structures confirmed pentagonal bipyramidal geometry for all studied complexes with a strong Jahn-Teller distortion in the pentagonal equatorial plane and significantly elongated Ni-O distance(s) with a decrease of this distortion by varying axial coligands (CH3CN > Br- > I- > NCS- > imidazole). Direct current magnetic measurements revealed the easy-axis type of magnetic anisotropy with negative as well as positive axial zero-field-splitting parameter D ranging from +6.8 to -14.5 cm(-1), which remains not affected in the halogenido series Cl- & RARR; Br- & RARR; I-, but which increases in the series with N-axial ligands in order CH3CN & RARR; NCS- & RARR; imidazole. Theoretical calculations helped to elucidate (i) the final coordination numbers 6 + 1 for 1 and 2, and 5 + 2 for 2-5, (ii) the pattern of splitting of d-orbitals, contributions of excited states to the final D-values and their final signs, and (iii) the complexity in the variation of the D and E parameters with elongation of axial bond distances in such strongly distorted systems. The studied complexes did not show any alternating magnetic susceptibility signal, but it was clearly documented that the magnetic anisotropy of the pentagonal bipyramidal Ni(ii) complexes can be modulated/tuned by variation of axial coligands. Nevertheless, great care has to be taken for symmetry of the equatorial ligand field.
Název v anglickém jazyce
Effective tuning of magnetic anisotropy in distorted pentagonal bipyramidal Ni(ii) complexes via substitution of axial coligands
Popis výsledku anglicky
A series of Ni(ii) complexes with pyridine-based macrocyclic ligand L (3,12,18-triaza-6,9-dioxabicyclo[12.3.1]octadeca-1(18),14,16-triene) with general formula [Ni(L)(X)(2)](0/2+) (X = Br- (1), I- (2), CH3CN (3), NCS- (4), imidazole (5)) was prepared and thoroughly investigated. X-ray molecular structures confirmed pentagonal bipyramidal geometry for all studied complexes with a strong Jahn-Teller distortion in the pentagonal equatorial plane and significantly elongated Ni-O distance(s) with a decrease of this distortion by varying axial coligands (CH3CN > Br- > I- > NCS- > imidazole). Direct current magnetic measurements revealed the easy-axis type of magnetic anisotropy with negative as well as positive axial zero-field-splitting parameter D ranging from +6.8 to -14.5 cm(-1), which remains not affected in the halogenido series Cl- & RARR; Br- & RARR; I-, but which increases in the series with N-axial ligands in order CH3CN & RARR; NCS- & RARR; imidazole. Theoretical calculations helped to elucidate (i) the final coordination numbers 6 + 1 for 1 and 2, and 5 + 2 for 2-5, (ii) the pattern of splitting of d-orbitals, contributions of excited states to the final D-values and their final signs, and (iii) the complexity in the variation of the D and E parameters with elongation of axial bond distances in such strongly distorted systems. The studied complexes did not show any alternating magnetic susceptibility signal, but it was clearly documented that the magnetic anisotropy of the pentagonal bipyramidal Ni(ii) complexes can be modulated/tuned by variation of axial coligands. Nevertheless, great care has to be taken for symmetry of the equatorial ligand field.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10402 - Inorganic and nuclear chemistry
Návaznosti výsledku
Projekt
<a href="/cs/project/LO1305" target="_blank" >LO1305: Rozvoj centra pokročilých technologií a materiálů</a><br>
Návaznosti
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Ostatní
Rok uplatnění
2022
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Dalton Transactions
ISSN
1477-9226
e-ISSN
1477-9234
Svazek periodika
51
Číslo periodika v rámci svazku
47
Stát vydavatele periodika
GB - Spojené království Velké Británie a Severního Irska
Počet stran výsledku
12
Strana od-do
18033-18044
Kód UT WoS článku
000885052400001
EID výsledku v databázi Scopus
2-s2.0-85142606003