Two Types of Hexanuclear Partial Tetracubane [Ni(4)Ln(2)] (Ln = Dy, Tb, Ho) Complexes of Thioether-Based Schiff Base Ligands: Synthesis, Structure, and Comparison of Magnetic Properties

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F19%3A73596429" target="_blank" >RIV/61989592:15310/19:73596429 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.9b01517" target="_blank" >https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.9b01517</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.9b01517" target="_blank" >10.1021/acs.inorgchem.9b01517</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Two Types of Hexanuclear Partial Tetracubane [Ni(4)Ln(2)] (Ln = Dy, Tb, Ho) Complexes of Thioether-Based Schiff Base Ligands: Synthesis, Structure, and Comparison of Magnetic Properties

Popis výsledku v původním jazyce

New Schiff base ligand H2L containing N2O4S donor atoms has been explored for its ability to provide complexes of selected 3d and 4f metal ions. Room temperature reaction of H2L with NiCl2 center dot 6H(2)O and Ln(NO3)(3)center dot 5H(2)O in the presence of Et3N in MeCN-MeOH (2:1) medium resulted in [Ni(4)Ln(2)(L)(2)(mu-Cl)(2)(mu(3)-OH)(4)(H2O)(6)]Cl-4 center dot 2H(2)O (where Ln = Dy3+ (1), Tb3+ (2), and Ho3+ (3) and H2L = 2-(2-(2-(2-hydroxy-3-methoxybenzylideneamino)ethylthio)ethylimino)methyl)-6-methoxyphenol). Use of Ni(SCN)(2)center dot 4H(2)O during synthesis provided SCN- ions for bridging and terminal coordination in [Ni(4)Ln(2)(L)(2)(mu-NCS)(2)(mu(3)-OH)(4) (NCS)(4) (H2O)(2)]center dot XMeOH center dot yH(2)O (where Ln = Dy3+ (4), x = 2, y = 4; Tb3+ (5) and Ho3+ (6), x = 0, y = 14.1). All six complexes possess a hexanuclear defective tetracubane topology having exchangeable bridging groups. The study of direct current magnetic susceptibility measurements revealed that the Ni(II) ions are engaged in ferromagnetic interaction with the Dy-III, Tb-III and Ho-III ions and have significant magnetic anisotropy in all six complexes. Alternating current susceptibility measurements confirmed that both of the two types of compounds qualify as zero-field single molecule magnets (SMMs), and the effective barrier for the reversal of the magnetic moment was found to be in the range U-eff = 23-31 K for 1-2 and 4-5, respectively. Detailed insight into the electronic structure and magnetic properties was calculated using DFT- and CASSCF-based analyses. The found isotropic exchange parameter (I) values are J(Ni-Ni) = -4.7 cm(-1) for 1 and J(Ni-Ni) = +29.2 cm(-1) for 4 and clearly indicate that the mu-NCS-bridge is a better candidate than mu-Cl for ferromagnetic exchange interactions. Out of the six complexes, only complex 5 displays Tb-III centered emission peaks at 451 and 480 nm.

Název v anglickém jazyce

Two Types of Hexanuclear Partial Tetracubane [Ni(4)Ln(2)] (Ln = Dy, Tb, Ho) Complexes of Thioether-Based Schiff Base Ligands: Synthesis, Structure, and Comparison of Magnetic Properties

Popis výsledku anglicky

New Schiff base ligand H2L containing N2O4S donor atoms has been explored for its ability to provide complexes of selected 3d and 4f metal ions. Room temperature reaction of H2L with NiCl2 center dot 6H(2)O and Ln(NO3)(3)center dot 5H(2)O in the presence of Et3N in MeCN-MeOH (2:1) medium resulted in [Ni(4)Ln(2)(L)(2)(mu-Cl)(2)(mu(3)-OH)(4)(H2O)(6)]Cl-4 center dot 2H(2)O (where Ln = Dy3+ (1), Tb3+ (2), and Ho3+ (3) and H2L = 2-(2-(2-(2-hydroxy-3-methoxybenzylideneamino)ethylthio)ethylimino)methyl)-6-methoxyphenol). Use of Ni(SCN)(2)center dot 4H(2)O during synthesis provided SCN- ions for bridging and terminal coordination in [Ni(4)Ln(2)(L)(2)(mu-NCS)(2)(mu(3)-OH)(4) (NCS)(4) (H2O)(2)]center dot XMeOH center dot yH(2)O (where Ln = Dy3+ (4), x = 2, y = 4; Tb3+ (5) and Ho3+ (6), x = 0, y = 14.1). All six complexes possess a hexanuclear defective tetracubane topology having exchangeable bridging groups. The study of direct current magnetic susceptibility measurements revealed that the Ni(II) ions are engaged in ferromagnetic interaction with the Dy-III, Tb-III and Ho-III ions and have significant magnetic anisotropy in all six complexes. Alternating current susceptibility measurements confirmed that both of the two types of compounds qualify as zero-field single molecule magnets (SMMs), and the effective barrier for the reversal of the magnetic moment was found to be in the range U-eff = 23-31 K for 1-2 and 4-5, respectively. Detailed insight into the electronic structure and magnetic properties was calculated using DFT- and CASSCF-based analyses. The found isotropic exchange parameter (I) values are J(Ni-Ni) = -4.7 cm(-1) for 1 and J(Ni-Ni) = +29.2 cm(-1) for 4 and clearly indicate that the mu-NCS-bridge is a better candidate than mu-Cl for ferromagnetic exchange interactions. Out of the six complexes, only complex 5 displays Tb-III centered emission peaks at 451 and 480 nm.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

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)

Rok uplatnění

2019

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

—

Svazek periodika

58

Číslo periodika v rámci svazku

18

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

15

Strana od-do

12184-12198

Kód UT WoS článku

000486565600037

EID výsledku v databázi Scopus

2-s2.0-85072234317