Dataset Information

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes.

ABSTRACT: The exchange coupling, represented by the J 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.

SUBMITTER: Ziolkowska A

PROVIDER: S-EPMC9959031 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes.

Ziółkowska Aleksandra A Witwicki Maciej M

International journal of molecular sciences 20230216 4

The exchange coupling, represented by the <i>J</i> 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 ...[more]

PMID: 36835412

Similar Datasets

Project description:The concurrent effects of single-ion anisotropy and exchange interactions on the electronic structure and magnetization dynamics have been analyzed for a cobalt(ii)-semiquinonate complex. Analogs containing diamagnetic catecholate and tropolonate ligands were employed for comparison of the magnetic behavior and zinc congeners assisted with the spectroscopic characterization and assessment of intermolecular interactions in the cobalt(ii) compounds. Low temperature X-band (? ? 9.4 GHz) and W-Band (? ? 94 GHz) electron paramagnetic resonance spectroscopy and static and dynamic magnetic measurements have been used to elucidate the electronic structure of the high spin cobalt(ii) ion in [Co(Me3tpa)(Br4cat)] (1; Me3tpa = tris[(6-methyl-2-pyridyl)methyl]amine, Br4cat2- = tetrabromocatecholate) and [Co(Me3tpa)(trop)](PF6) (2(PF6); trop- = tropolonate), which show slow relaxation of the magnetization in applied field. The cobalt(ii)-semiquinonate exchange interaction in [Co(Me3tpa)(dbsq)](PF6)·tol (3(PF6)·tol; dbsq- = 3,5-di-tert-butylsemiquinonate, tol = toluene) has been determined using an anisotropic exchange Hamiltonian in conjunction with multistate restricted active space self-consistent field ab initio modeling and wavefunction analysis, with comparison to magnetic and inelastic neutron scattering data. Our results demonstrate dominant ferromagnetic exchange for 3+ that is of similar magnitude to the anisotropy parameters of the cobalt(ii) ion and contains a significant contribution from spin-orbit coupling. The nature of the exchange coupling between octahedral high spin cobalt(ii) and semiquinonate ligands is a longstanding question; answering this question for the specific case of 3+ has confirmed the considerable sensitivity of the exchange to the molecular structure. The methodology employed will be generally applicable for elucidating exchange coupling between orbitally-degenerate metal ions and radical ligands and relevant to the development of bistable molecules and their integration into devices.

Dataset Information

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes.

Publications

Understanding the Exchange Interaction between Paramagnetic Metal Ions and Radical Ligands: DFT and Ab Initio Study on Semiquinonato Cu(II) Complexes.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets