Beyond the Classical Contributions to Exchange Coupling in Binuclear Transition Metal Complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F21%3A00541747" target="_blank" >RIV/61388963:_____/21:00541747 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388955:_____/21:00541747

Výsledek na webu

<a href="https://doi.org/10.1021/acs.jpca.0c11237" target="_blank" >https://doi.org/10.1021/acs.jpca.0c11237</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.0c11237" target="_blank" >10.1021/acs.jpca.0c11237</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Beyond the Classical Contributions to Exchange Coupling in Binuclear Transition Metal Complexes

Popis výsledku v původním jazyce

Complexes with two or more magnetically coupled metal ions have attracted considerable attention as catalysts of many vital processes, single-molecule magnets, or spin-crossover compounds. Elucidation of their electronic structures is essential for understanding their catalytic and magnetic properties. Here, we provide an unprecedented insight into exchange-coupling mechanisms between the magnetic centers in six prototypical bis-μ-oxo bimetallic M2O2 complexes, including two biologically relevant models of non-heme iron enzymes. Employing multiconfigurational/multireference methods and related orbital entanglement analysis, we revealed the essential and counterintuitive role of predominantly unoccupied valence metal d orbitals in their strong antiferromagnetic coupling. We found that the participation of these orbitals is twofold. First, they enhance the superexchange between the singly occupied d orbitals. Second, they become substantially occupied and thus directly magnetically active, which we perceive as a new mechanism of the exchange interaction between the magnetic transition metal centers.

Název v anglickém jazyce

Beyond the Classical Contributions to Exchange Coupling in Binuclear Transition Metal Complexes

Popis výsledku anglicky

Complexes with two or more magnetically coupled metal ions have attracted considerable attention as catalysts of many vital processes, single-molecule magnets, or spin-crossover compounds. Elucidation of their electronic structures is essential for understanding their catalytic and magnetic properties. Here, we provide an unprecedented insight into exchange-coupling mechanisms between the magnetic centers in six prototypical bis-μ-oxo bimetallic M2O2 complexes, including two biologically relevant models of non-heme iron enzymes. Employing multiconfigurational/multireference methods and related orbital entanglement analysis, we revealed the essential and counterintuitive role of predominantly unoccupied valence metal d orbitals in their strong antiferromagnetic coupling. We found that the participation of these orbitals is twofold. First, they enhance the superexchange between the singly occupied d orbitals. Second, they become substantially occupied and thus directly magnetically active, which we perceive as a new mechanism of the exchange interaction between the magnetic transition metal centers.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

1520-5215

Svazek periodika

125

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

2276-2283

Kód UT WoS článku

000635440800007

EID výsledku v databázi Scopus

2-s2.0-85103606434