Ancillary Ligand Coordination Directed Modes of Aggregation in Mixed-Valence Tetranuclear Cobalt Complexes: Synthesis, Structure, Field-Induced SIM Behavior, and Theoretical Insights
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F23%3A73621973" target="_blank" >RIV/61989592:15310/23:73621973 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.2c01192" target="_blank" >https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.2c01192</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.cgd.2c01192" target="_blank" >10.1021/acs.cgd.2c01192</a>
Alternative languages
Result language
angličtina
Original language name
Ancillary Ligand Coordination Directed Modes of Aggregation in Mixed-Valence Tetranuclear Cobalt Complexes: Synthesis, Structure, Field-Induced SIM Behavior, and Theoretical Insights
Original language description
The contrasting metal-ion coordination reactivity behavior for the multisite ligand H3L ([2,6-bis-{(2-hydroxymethyl-phenylimino)methyl}-4-methylphenol]) with Co(ClO4)2 center dot 6H2O in the presence of ancillary ligands NaPiv (Piv = (CH3)3CCO2-) and NH4SCN afforded two different types of mixed-valence tetranuclear cobalt complexes, [CoIII3CoII(HL)(L)(mu 4-O)(mu-OH)-((CH3)3CCOO)2]ClO4 center dot H2O (1) and [CoIII2CoII2(L)2(NCS)4- (CH3CN)2]center dot CH3CN (2). In the first case, the presence of bridging pivalate anions triggered the oxido-hydroxido-bridged dual control for aggregation, whereas in the second case, terminal thiocyanate coordination forced the dicubane type of aggregation. The connectivity for different numbers of CoIII and CoII ions are achieved through contrasting bridges by ancillary water-molecule-derived HO- plus O2- linkers and ligand-anion-based double phenolato bridges, where terminal monodentate coordinations finally fulfill the octahedral geometries around the CoII ions. Alternating current/direct current (AC/DC) magnetic studies revealed field-induced slow magnetic relaxation for complex 1 that arises from the single octahedral CoII ion connected to three other diamagnetic CoIII ions. Whereas in complex 2, having a tetranuclear CoIII2CoII2 structure, the two CoII centers showed an antiferromagnetic interaction (J = -0.39 cm-1). The structural distortions in these two types of aggregates lead to different magnitudes of easy-axis magnetic anisotropy (D = -51.31 cm-1 for 1 and -31.9 cm-1 for 2) and a small but non-negligible transverse component (E/D = 0.263 for 1 and 0.255 for 2). The static and dynamic magnetic data were analyzed using DFT and CASSCF-based calculations.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
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
CRYSTAL GROWTH & DESIGN
ISSN
1528-7483
e-ISSN
1528-7505
Volume of the periodical
23
Issue of the periodical within the volume
4
Country of publishing house
US - UNITED STATES
Number of pages
13
Pages from-to
2169-2181
UT code for WoS article
000942358300001
EID of the result in the Scopus database
2-s2.0-85149144079