Effective tuning of magnetic anisotropy in distorted pentagonal bipyramidal Ni(ii) complexes via substitution of axial coligands
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Effective tuning of magnetic anisotropy in distorted pentagonal bipyramidal Ni(ii) complexes via substitution of axial coligands
Original language description
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.
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
<a href="/en/project/LO1305" target="_blank" >LO1305: Development of the center of advanced technologies and materials</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2022
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
1477-9234
Volume of the periodical
51
Issue of the periodical within the volume
47
Country of publishing house
GB - UNITED KINGDOM
Number of pages
12
Pages from-to
18033-18044
UT code for WoS article
000885052400001
EID of the result in the Scopus database
2-s2.0-85142606003