Mn(III)-Salen Complexes with Metallophilic Interactions

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F23%3A73622012" target="_blank" >RIV/61989592:15310/23:73622012 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.mdpi.com/2073-4352/13/8/1217" target="_blank" >https://www.mdpi.com/2073-4352/13/8/1217</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.3390/cryst13081217" target="_blank" >10.3390/cryst13081217</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Mn(III)-Salen Complexes with Metallophilic Interactions

Popis výsledku v původním jazyce

We synthesized a series of five novel Mn-salen-based compounds (1a-1c, 2a, 2b) through the reaction between precursor chloride complexes and potassium silver/gold dicyanide. The prepared compounds were structurally and magnetically characterized. Our findings revealed that all the Mn(III) central atoms exhibited an axially elongated coordination polyhedron, leading to the observation of axial magnetic anisotropy as indicated by the negative axial magnetic parameter D, which was determined through fitting the experimental magnetic data and supported by theoretical CASSCF/NEVPT2 calculations. Furthermore, we observed magnetic-exchange interactions only in compounds with a special supramolecular topology involving O-H···O hydrogen-bonded dimers. In these cases, the weak magnetic exchange (J/cm(-1) = -0.58(2) in 1b and -0.73(7) in 2b) was mediated by the O-H···O hydrogen bonds. These findings were further supported by BS-DFT calculations, which predicted weak antiferromagnetic exchanges in these complexes and ruled out exchange interactions mediated by diamagnetic cyanido metallo-complex bridges. Additionally, we investigated the observed Ag···π (1b) and Au ···Au (2b) interactions using QT-AIM calculations, confirming their non-covalent nature. We compared these results with previously reported Mn-salen-based compounds with metallophilic interactions arising from the presence of the [Ag/Au(CN)(2)](-) bridging units.

Název v anglickém jazyce

Mn(III)-Salen Complexes with Metallophilic Interactions

Popis výsledku anglicky

We synthesized a series of five novel Mn-salen-based compounds (1a-1c, 2a, 2b) through the reaction between precursor chloride complexes and potassium silver/gold dicyanide. The prepared compounds were structurally and magnetically characterized. Our findings revealed that all the Mn(III) central atoms exhibited an axially elongated coordination polyhedron, leading to the observation of axial magnetic anisotropy as indicated by the negative axial magnetic parameter D, which was determined through fitting the experimental magnetic data and supported by theoretical CASSCF/NEVPT2 calculations. Furthermore, we observed magnetic-exchange interactions only in compounds with a special supramolecular topology involving O-H···O hydrogen-bonded dimers. In these cases, the weak magnetic exchange (J/cm(-1) = -0.58(2) in 1b and -0.73(7) in 2b) was mediated by the O-H···O hydrogen bonds. These findings were further supported by BS-DFT calculations, which predicted weak antiferromagnetic exchanges in these complexes and ruled out exchange interactions mediated by diamagnetic cyanido metallo-complex bridges. Additionally, we investigated the observed Ag···π (1b) and Au ···Au (2b) interactions using QT-AIM calculations, confirming their non-covalent nature. We compared these results with previously reported Mn-salen-based compounds with metallophilic interactions arising from the presence of the [Ag/Au(CN)(2)](-) bridging units.

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

2023

Kód důvěrnosti údajů

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

Název periodika

Crystals

ISSN

2073-4352

e-ISSN

—

Svazek periodika

13

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

15

Strana od-do

"1217-1"-"1217-15"

Kód UT WoS článku

001056732900001

EID výsledku v databázi Scopus

2-s2.0-85169162449