Repozytorium
Wyszukaj
Kolekcje
Inne
Synthesis, Characterization, Magnetic Properties, and Electrocatalytic Activities of a Series of Tetranuclear Fe(III) Clusters
Autorzy
Rok wydania
2026
Czasopismo
Numer woluminu
26
Strony
6996-7016
DOI
10.1021/acs.cgd.6c00612
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
In this research, a new series of tetranuclear Fe(III) clusters (1–3) represented by the general formula [Fe4(L)2(μ2-O)(μ2–OH)(μ2-p-O2CC6H4(R))2](ClO4)·H2O were designed and synthesized. The synthesis involves the reaction of a multidentate ligand, H3L, with Fe(ClO4)2·6H2O, in combination with p-chlorobenzoic acid, p-nitrobenzoic acid, and p-methylbenzoic acid (H3L = N,N′-bis[2-carboxybenzomethyl]-N,N′-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol; R = Cl (1), NO2 (2), and CH3 (3)). Clusters 1–3 were characterized by multiple analytical techniques, including single-crystal X-ray diffraction (SCXRD) analysis. As revealed by SCXRD analysis, the molecular structures of 1–3 contain two crystallographically equivalent [Fe2L]3+ species, which are interlinked by one μ2-O2– and μ2–OH–, and two auxiliary μ2-p-O2CC6H4(R)− ligands, generating concave-shaped, fascinating rectangular architectures. The magnetic susceptibility data of 1–3 were measured and analyzed by employing variable-temperature SQUID magnetometry between 1.8 and 300 K, demonstrating the occurrence of intramolecular antiferromagnetic exchange interactions among the Fe(III) ions. These Fe4 clusters holding the redox-flexible multimetallic cores worked well for water splitting. They showed low overpotential values of 177–229 mV for the hydrogen evolution reaction (HER) and 310–478 mV for the oxygen evolution reaction (OER) to achieve a current density of 10 mA/cm2. Essentially, in clusters 1–3, the occurrence of Fe···Fe synergistic effect and appropriately located activation sites greatly favor the formation of intramolecular H–H and O–O bonds. Density functional theory (DFT) computations validate the proposed mechanistic pathways of HER and OER processes.
Słowa kluczowe
Electrocatalysts, Magnetic properties, Evolution reactions, Cluster chemistry, Radiology
Adres publiczny
http://dx.doi.org/10.1021/acs.cgd.6c00612
Strona internetowa wydawcy
Podobne publikacje
Activation and adsorption of multiple H2 molecules on a Pd5 cluster: a density functional study.
Moc Jerzy, Musaev D. G., Morokuma K.
Characterization of highly efficient RNA-cleaving DNAzymes that function ar acidic pH with no divalent metal-ion cofactors.
Kasprowicz Aleksandra, Stokowa-Sołtys Kamila, Jeżowska-Bojczuk Małgorzata, Wrzesiński Jan, Ciesiołka Jerzy
Toward understanding the electron density distribution in magnetic clusters : insight from the ELF and AIM analyses of ground-state Fe4.
Berski Sławomir, Gutsev G. L., Mochena M. D., Andrés Juan