Tuning Self-Aggregation and Nuclearity in Multinuclear CoII Complexes: Synthesis, Structural Diversity, and Changes in Magnetic Anisotropy and Relaxation Behavior

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F25%3A73633969" target="_blank" >RIV/61989592:15310/25:73633969 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.cgd.5c00337" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.cgd.5c00337</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.cgd.5c00337" target="_blank" >10.1021/acs.cgd.5c00337</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Tuning Self-Aggregation and Nuclearity in Multinuclear CoII Complexes: Synthesis, Structural Diversity, and Changes in Magnetic Anisotropy and Relaxation Behavior

Popis výsledku v původním jazyce

The reaction of HL (2,6-bis-[{(methylthio)phenylimino}methyl]-4-methylphenol) with [Co2(mu-OH2)(O2CCMe3)4(HO2CCMe3)4] (Co 2 -Piv) in MeCN provided a trinuclear triangular-type complex [Co3L(mu 3-OH)(mu 1,3-O2CCMe3)3(O2CCMe3)]&lt;middle dot&gt;MeCN (1), whereas in another reaction, using Co(ClO4)2&lt;middle dot&gt;6H2O as the source of CoII ions with the additional employment of NaOAc in MeOH resulted in a tetranuclear cubane-type complex [Co4L2(mu 3-OH)(mu 3-OMe)(mu 1,3-CH3CO2)2](ClO4)2&lt;middle dot&gt;2.5H2O (2). The varying coordination behavior of the ligand was facilitated using two different CoII salts and the availability of different bridging anions, and the solvent medium used prompted two types of aggregations. Complex 1 has two CoII ions bound in the two adjacent pockets of L- in nearly octahedral geometry and one pivalate anion entangled tetrahedral CoII center. Complex 2 has four CoII centers, all having nearly octahedral geometry. From the alternating current (AC) susceptibility measurements, slow relaxation of magnetization for 1 becomes apparent on application of a DC field, but 2 does not exhibit slow magnetic relaxation, regardless of the applied DC field strength. The CASSCF/NEVPT2 calculations disclosed that the octahedral CoII sites in both 1 and 2 have easy-plane magnetic anisotropy of D in the +56.46-63.8 cm-1 range and the transverse component |E| in the 4.96-12.95 cm-1 range. The unique tetrahedral CoII center in 1 holds D = -6.46 cm-1 and |E| = 0.027 cm-1 with a negligible predisposition for quantum tunneling of magnetization, reinforcing the occurrence of field-induced slow magnetic relaxation of 1.

Název v anglickém jazyce

Tuning Self-Aggregation and Nuclearity in Multinuclear CoII Complexes: Synthesis, Structural Diversity, and Changes in Magnetic Anisotropy and Relaxation Behavior

Popis výsledku anglicky

The reaction of HL (2,6-bis-[{(methylthio)phenylimino}methyl]-4-methylphenol) with [Co2(mu-OH2)(O2CCMe3)4(HO2CCMe3)4] (Co 2 -Piv) in MeCN provided a trinuclear triangular-type complex [Co3L(mu 3-OH)(mu 1,3-O2CCMe3)3(O2CCMe3)]&lt;middle dot&gt;MeCN (1), whereas in another reaction, using Co(ClO4)2&lt;middle dot&gt;6H2O as the source of CoII ions with the additional employment of NaOAc in MeOH resulted in a tetranuclear cubane-type complex [Co4L2(mu 3-OH)(mu 3-OMe)(mu 1,3-CH3CO2)2](ClO4)2&lt;middle dot&gt;2.5H2O (2). The varying coordination behavior of the ligand was facilitated using two different CoII salts and the availability of different bridging anions, and the solvent medium used prompted two types of aggregations. Complex 1 has two CoII ions bound in the two adjacent pockets of L- in nearly octahedral geometry and one pivalate anion entangled tetrahedral CoII center. Complex 2 has four CoII centers, all having nearly octahedral geometry. From the alternating current (AC) susceptibility measurements, slow relaxation of magnetization for 1 becomes apparent on application of a DC field, but 2 does not exhibit slow magnetic relaxation, regardless of the applied DC field strength. The CASSCF/NEVPT2 calculations disclosed that the octahedral CoII sites in both 1 and 2 have easy-plane magnetic anisotropy of D in the +56.46-63.8 cm-1 range and the transverse component |E| in the 4.96-12.95 cm-1 range. The unique tetrahedral CoII center in 1 holds D = -6.46 cm-1 and |E| = 0.027 cm-1 with a negligible predisposition for quantum tunneling of magnetization, reinforcing the occurrence of field-induced slow magnetic relaxation of 1.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

CRYSTAL GROWTH &amp; DESIGN

ISSN

1528-7483

e-ISSN

1528-7505

Svazek periodika

25

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

3915-3927

Kód UT WoS článku

001493294100001

EID výsledku v databázi Scopus

2-s2.0-105005799752