Lanthanoid coordination prompts unusually distorted pseudo-octahedral NiII coordination in heterodinuclear Ni-Ln complexes: synthesis, structure and understanding of magnetic behaviour through experiment and computation
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F23%3A73622013" target="_blank" >RIV/61989592:15310/23:73622013 - isvavai.cz</a>
Result on the web
<a href="https://pubs.rsc.org/en/content/articlelanding/2023/dt/d3dt01387a" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2023/dt/d3dt01387a</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d3dt01387a" target="_blank" >10.1039/d3dt01387a</a>
Alternative languages
Result language
angličtina
Original language name
Lanthanoid coordination prompts unusually distorted pseudo-octahedral NiII coordination in heterodinuclear Ni-Ln complexes: synthesis, structure and understanding of magnetic behaviour through experiment and computation
Original language description
In this work, a new family of binuclear Ni-II-Ln(III) complexes with the formula [NiLn(L)(2)(NO3)(3)]0.5H(2)O (Ln = Gd, 1; Tb, 2; Dy, 3; Ho, 4; Er, 5; Yb, 6; Y, 7) was synthesized using a thioether group-bearing Schiff base. Due to the strict hard/soft dichotomy between the 4f and 3d metal ions, selective coordination of Ni-II and 4f metal ions was achieved with the adjacent soft ONS and hard OO binding pockets of the ligand. All the complexes 1-7 exhibit a Ni-II centre in a distorted pseudo-octahedral geometry with the Ln(III) centres in distorted bicapped square-antiprism geometry. The huge distortion around the Ni-II centres is triggered for the accommodation of larger lanthanoids to the adjacent OO coordination site, and this forces the Ni-II centres to have a tridentate coordination from the ONS, as intermediate between meridional and facial binding. Field-induced single-molecule magnetic behaviour was observed for heterodinuclear complexes involving Kramers lanthanide ions (Ln(III) = Dy, Er and Yb), with magnetic relaxation occurring through an Orbach process only for 5. DFT calculations using various functionals (BP86, B3LYP, PBE0, TPSSh, PWPB95, R(2)SCAN) were applied to calculate the isotropic exchange, showing good agreement with the experiment (J(Gd-Ni) = +1.78 cm(-1)). CASSCF calculations for Ni-II and Ln(III) ions were also performed to reveal detailed information about their electronic structure and magnetic anisotropy, supporting the experimental observations. This study accentuates the mutual distortion of coordination geometry induced by flexibility of the ligand backbone with the simultaneous binding of two different metal ions.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
—
Continuities
S - Specificky vyzkum na vysokych skolach
Others
Publication year
2023
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
52
Issue of the periodical within the volume
30
Country of publishing house
GB - UNITED KINGDOM
Number of pages
13
Pages from-to
10402-10414
UT code for WoS article
001027899500001
EID of the result in the Scopus database
2-s2.0-85166213889