Tuning Self-Aggregation and Nuclearity in Multinuclear CoII Complexes: Synthesis, Structural Diversity, and Changes in Magnetic Anisotropy and Relaxation Behavior
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Tuning Self-Aggregation and Nuclearity in Multinuclear CoII Complexes: Synthesis, Structural Diversity, and Changes in Magnetic Anisotropy and Relaxation Behavior
Original language description
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)]<middle dot>MeCN (1), whereas in another reaction, using Co(ClO4)2<middle dot>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<middle dot>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.
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
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
CRYSTAL GROWTH & DESIGN
ISSN
1528-7483
e-ISSN
1528-7505
Volume of the periodical
25
Issue of the periodical within the volume
11
Country of publishing house
US - UNITED STATES
Number of pages
13
Pages from-to
3915-3927
UT code for WoS article
001493294100001
EID of the result in the Scopus database
2-s2.0-105005799752