Integration of Diamagnetic and Paramagnetic NiII Ions and Atmospheric CO2 Fixation in Ni4Ln2 Complexes: Exploring Slow Magnetic Relaxation and Sustainable Catalysis for Epoxide Cycloaddition
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F25%3A73633987" target="_blank" >RIV/61989592:15310/25:73633987 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5c03509" target="_blank" >https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5c03509</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.5c03509" target="_blank" >10.1021/acs.inorgchem.5c03509</a>
Alternative languages
Result language
angličtina
Original language name
Integration of Diamagnetic and Paramagnetic NiII Ions and Atmospheric CO2 Fixation in Ni4Ln2 Complexes: Exploring Slow Magnetic Relaxation and Sustainable Catalysis for Epoxide Cycloaddition
Original language description
We report the synthesis and characterization of a new Schiff base ligand (HL), derived from 2-picolylamine and 2-hydroxy-3-methoxy-5-methylbenzaldehyde. Its reaction with Ni(NO3)2<middle dot>6H2O and Ln(NO3)3<middle dot>xH2O (Ln = GdIII, TbIII, DyIII) in the presence of triethylamine affords a carbonato-bridged family of heterobimetallic Ni4Ln2 complexes: [Ni4Ln2(L)2(L ')2(mu-CO3)2(NO3)2]<middle dot>xMeOH<middle dot>yH2O (1-3). During the complexation reaction, ligand HL undergoes an in situ oxidation, followed by C-C coupling to generate a secondary ligand (H3L '). A similar transformation of the ligand was also observed in the isolated square planar NiII complex [Ni(HL ')]<middle dot>1.5MeOH<middle dot>0.5H2O. X-ray crystallography confirms that 1-3 are isomorphous, featuring a rare combination of both paramagnetic and diamagnetic NiII ions. The magnetic measurements reveal an intramolecular NiII-LnIII ferromagnetic interaction and slow relaxation of magnetization in all three complexes, further supported by DFT and ab initio studies. Beyond magnetism, these complexes act as efficient catalysts for the fixation of CO2 into cyclic carbonates. Epoxide conversion proceeds with low catalyst loading, affording high yields (82-98%) at 70-100 degrees C within 4-6 h. Gram-scale reactions validate practical utility, while green metrics highlight sustainability (E-factor 3.73, excellent Eco-scale). Substrate scope includes aliphatic, phenoxyalkyl, and disubstituted oxiranes. Mechanistic insights underscore the cooperative roles of NiII and LnIII centers, providing valuable guidelines for designing multifunctional catalysts for sustainable CO2 utilization.
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
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
INORGANIC CHEMISTRY
ISSN
0020-1669
e-ISSN
1520-510X
Volume of the periodical
64
Issue of the periodical within the volume
37
Country of publishing house
US - UNITED STATES
Number of pages
19
Pages from-to
19094-19112
UT code for WoS article
001567404300001
EID of the result in the Scopus database
2-s2.0-105016629985