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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

S - Specificky vyzkum na vysokych skolach

Rok uplatnění

2023

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

52

Číslo periodika v rámci svazku

30

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

13

Strana od-do

10402-10414

Kód UT WoS článku

001027899500001

EID výsledku v databázi Scopus

2-s2.0-85166213889