Spin Crossover in Iron(II) Porphyrazine Induced by Noncovalent Interactions Combined with Hybridization of Iron(II) Porphyrazine and Ligand's Orbitals: CASPT2, CCSD(T), and DFT Studies

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F19%3A00509721" target="_blank" >RIV/61388963:_____/19:00509721 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989592:15310/19:73595485

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.jpcc.9b05352" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jpcc.9b05352</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpcc.9b05352" target="_blank" >10.1021/acs.jpcc.9b05352</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Spin Crossover in Iron(II) Porphyrazine Induced by Noncovalent Interactions Combined with Hybridization of Iron(II) Porphyrazine and Ligand's Orbitals: CASPT2, CCSD(T), and DFT Studies

Popis výsledku v původním jazyce

Spin crossover processes invoked by external stimuli, e.g., temperature, pressure, irradiation with light, electric or magnetic field, as well as formation of dative bond, are well-known phenomena. The effect of weak noncovalent interactions on spin crossover is, however, much less explored. To improve understanding of the origin of spin crossover processes driven by noncovalent interactions, the multireference and density functional theory calculations are performed on iron(II) porphyrazine complexes with CO, NO, benzene, and pyridinyl radicals. The electron structure analyses are performed to discuss the differences in the nature of covalent and noncovalent bonding of CO and NO in axial and parallel orientations, respectively, as well as noncovalent bonding of benzene and pyridinyl radical with iron(II) porphyrazine. It is shown that the weak intermixing between the d orbitals of the metal center and suitably oriented p-orbitals of N-containing ligands are responsible for their stronger influence on the spin crossover compared to those CO and benzene ligands.

Název v anglickém jazyce

Spin Crossover in Iron(II) Porphyrazine Induced by Noncovalent Interactions Combined with Hybridization of Iron(II) Porphyrazine and Ligand's Orbitals: CASPT2, CCSD(T), and DFT Studies

Popis výsledku anglicky

Spin crossover processes invoked by external stimuli, e.g., temperature, pressure, irradiation with light, electric or magnetic field, as well as formation of dative bond, are well-known phenomena. The effect of weak noncovalent interactions on spin crossover is, however, much less explored. To improve understanding of the origin of spin crossover processes driven by noncovalent interactions, the multireference and density functional theory calculations are performed on iron(II) porphyrazine complexes with CO, NO, benzene, and pyridinyl radicals. The electron structure analyses are performed to discuss the differences in the nature of covalent and noncovalent bonding of CO and NO in axial and parallel orientations, respectively, as well as noncovalent bonding of benzene and pyridinyl radical with iron(II) porphyrazine. It is shown that the weak intermixing between the d orbitals of the metal center and suitably oriented p-orbitals of N-containing ligands are responsible for their stronger influence on the spin crossover compared to those CO and benzene ligands.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GX19-27454X" target="_blank" >GX19-27454X: Ovlivnění elektronických vlastností organometalických molekul pomocí jejich nekovalentních interakcí s rozpouštědly, ligandy a 2D nanosystémy</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry C

ISSN

1932-7447

e-ISSN

—

Svazek periodika

123

Číslo periodika v rámci svazku

37

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

23186-23194

Kód UT WoS článku

000487349600052

EID výsledku v databázi Scopus

2-s2.0-85072959377