Integration of Diamagnetic and Paramagnetic NiII Ions and Atmospheric CO2 Fixation in Ni4Ln2 Complexes: Exploring Slow Magnetic Relaxation and Sustainable Catalysis for Epoxide Cycloaddition

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Integration of Diamagnetic and Paramagnetic NiII Ions and Atmospheric CO2 Fixation in Ni4Ln2 Complexes: Exploring Slow Magnetic Relaxation and Sustainable Catalysis for Epoxide Cycloaddition

Popis výsledku v původním jazyce

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&lt;middle dot&gt;6H2O and Ln(NO3)3&lt;middle dot&gt;xH2O (Ln = GdIII, TbIII, DyIII) in the presence of triethylamine affords a carbonato-bridged family of heterobimetallic Ni4Ln2 complexes: [Ni4Ln2(L)2(L &apos;)2(mu-CO3)2(NO3)2]&lt;middle dot&gt;xMeOH&lt;middle dot&gt;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 &apos;). A similar transformation of the ligand was also observed in the isolated square planar NiII complex [Ni(HL &apos;)]&lt;middle dot&gt;1.5MeOH&lt;middle dot&gt;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.

Název v anglickém jazyce

Integration of Diamagnetic and Paramagnetic NiII Ions and Atmospheric CO2 Fixation in Ni4Ln2 Complexes: Exploring Slow Magnetic Relaxation and Sustainable Catalysis for Epoxide Cycloaddition

Popis výsledku anglicky

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&lt;middle dot&gt;6H2O and Ln(NO3)3&lt;middle dot&gt;xH2O (Ln = GdIII, TbIII, DyIII) in the presence of triethylamine affords a carbonato-bridged family of heterobimetallic Ni4Ln2 complexes: [Ni4Ln2(L)2(L &apos;)2(mu-CO3)2(NO3)2]&lt;middle dot&gt;xMeOH&lt;middle dot&gt;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 &apos;). A similar transformation of the ligand was also observed in the isolated square planar NiII complex [Ni(HL &apos;)]&lt;middle dot&gt;1.5MeOH&lt;middle dot&gt;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.

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

INORGANIC CHEMISTRY

ISSN

0020-1669

e-ISSN

1520-510X

Svazek periodika

64

Číslo periodika v rámci svazku

37

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

19

Strana od-do

19094-19112

Kód UT WoS článku

001567404300001

EID výsledku v databázi Scopus

2-s2.0-105016629985