The exchange coupling, represented by the parameter, is of tremendous importance in understanding the reactivity and magnetic behavior of open-shell molecular systems. In the past, it was the subject of theoretical investigations, but these studies are mostly limited to the interaction between metallic centers. The exchange coupling between paramagnetic metal ions and radical ligands has hitherto received scant attention in theoretical studies, and thus the understanding of the factors governing this interaction is lacking. In this paper, we use DFT, CASSCF, CASSCF/NEVPT2, and DDCI3 methods to provide insight into exchange interaction in semiquinonato copper(II) complexes. Our primary objective is to identify structural features that affect this magnetic interaction. We demonstrate that the magnetic character of Cu(II)-semiquinone complexes are mainly determined by the relative position of the semiquinone ligand to the Cu(II) ion. The results can support the experimental interpretation of magnetic data for similar systems and can be used for the in-silico design of magnetic complexes with radical ligands.
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http://dx.doi.org/10.3390/ijms24044001 | DOI Listing |
Chemistry
January 2025
VIT University, Materials Chemistry Division, School of Advanced Sciences, VIT University, 632014, Vellore, INDIA.
Amidines are a vital class of bioactive compounds and often necessitate multiple components for their synthesis. Therefore, exploring efficient and sustainable methodologies for their synthesis is indispensable. Herein, we disclose an alternative and greener method for synthesizing an unexplored new class of amidines through the photochemical synergistic effect of copper/nitroxyl radical catalysis.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Korea.
A series of Ni complexes bearing a redox and acid-base noninnocent tetraamido macrocyclic ligand, H-(TAML-4) {H-(TAML-4) = 15,15-dimethyl-5,8,13,17-tetrahydro-5,8,13,17-tetraaza-dibenzo[]cyclotridecene-6,7,14,16-tetraone}, with formal oxidation states of Ni, Ni, and Ni were synthesized and characterized structurally and spectroscopically. The X-ray crystallographic analysis of the Ni complexes revealed a square planar geometry, and the [Ni(TAML-4)] complex with the formal oxidation state of Ni was characterized to be [Ni(TAML-4)] with the oxidation state of the Ni ion and the one-electron oxidized TAML-4 ligand, TAML-4. The Ni oxidation state and the TAML-4 radical cation ligand, TAML-4, were supported by X-ray absorption spectroscopy and density functional theory calculations.
View Article and Find Full Text PDFJ Inorg Biochem
January 2025
Department of Chemistry, Karpagam Academy of Higher Education, Coimbatore 641 021, India; Centre for Material Chemistry, Karpagam Academy of Higher Education (Deemed to be University), Coimbatore 641 021, India. Electronic address:
A series of new Pd(II) complexes were synthesized from the reaction of andrographolide appended hydrazide derivatives with potassium tetrachloropalladate K[PdCl]. The formation of the complexes was confirmed through structural assessments conducted using various spectroscopic techniques. From the spectral studies we confirmed that the ligands coordinated to Pd(II) ion via amine nitrogen and enone oxygen.
View Article and Find Full Text PDFInorg Chem
January 2025
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, China.
The performance of energetic coordination compounds (ECCs) is influenced by their components and structure. Modifying the chemical structure of the ligands can balance the detonation performance and sensitivity. This study introduced Cu(3-PZCA)(ClO) () and Cu(2-IZCA)(ClO) (), using 3-PZCA and 2-IZCA as ligands.
View Article and Find Full Text PDFFront Immunol
January 2025
Department of General Surgery, The First Affiliated Hospital of Shandong First Medical University & Shandong Provincial Qianfoshan Hospital, Shandong, China.
Hepatoid adenocarcinoma of the stomach (HAS) is a rare subtype of gastric cancer characterized by histological features resembling hepatocellular carcinoma. Surgical intervention remains the preferred treatment modality for eligible patients. However, the efficacy of neoadjuvant therapy and alternative treatment regimens has been found to be suboptimal.
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