Spin-state versatility in FeII4L6 supramolecular cages with a pyridyl-hydrazone ligand scaffold modulated by solvents and counter anions

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F24%3A73627677" target="_blank" >RIV/61989592:15310/24:73627677 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2024/dt/d3dt02474a" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2024/dt/d3dt02474a</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d3dt02474a" target="_blank" >10.1039/d3dt02474a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Spin-state versatility in FeII4L6 supramolecular cages with a pyridyl-hydrazone ligand scaffold modulated by solvents and counter anions

Popis výsledku v původním jazyce

Discrete spin crossover (SCO) tetranuclear cages are a unique class of materials that have potential use in next-generation molecular recognition and sensing. In this work, two new edge-bridged SCO FeII4L(6) (L = 2,7-bis(((E)-pyridin-2-ylmethylene)amino)benzo[lmn] [3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone) supramolecular cages with different counter anions: ClO4- (2) and CF3SO3- (3) were constructed via subcomponent self-assembly to investigate both solvent and anion influences on their magnetic properties and compare them to cage 1 with a BF4- anion. Pyridyl-hydrazone bidentate ligand scaffolds were employed to replace the &apos;classical&apos; imidazole/thiazolyl-imine coordination units to induce SCO behaviour in these cages. 2 and 3 were structurally characterized by single-crystal X-ray diffraction analysis and electrospray ionization time-of-flight mass spectrometry. Magnetic susceptibilities of 1-3 and 1-3&lt;middle dot&gt;desolvated indicate that the solvents&apos; presence is in favor of the low-spin (LS) state. While different counter anions in 1-3&lt;middle dot&gt;desolvated affect the spin-state configurations of the four Fe-II metal centers. According to the Fe-57 M &amp; ouml;ssbauer spectral analysis, the spin-state distributions in 1-3 at 80 K are [2 high-spin (HS)-2LS], [1HS-3LS] and [2HS-2LS], respectively and density functional theory calculations were employed to investigate the reasons. These findings provide insights to regulate the spin-state versatility of SCO Fe-II cage systems in the solid state.

Název v anglickém jazyce

Spin-state versatility in FeII4L6 supramolecular cages with a pyridyl-hydrazone ligand scaffold modulated by solvents and counter anions

Popis výsledku anglicky

Discrete spin crossover (SCO) tetranuclear cages are a unique class of materials that have potential use in next-generation molecular recognition and sensing. In this work, two new edge-bridged SCO FeII4L(6) (L = 2,7-bis(((E)-pyridin-2-ylmethylene)amino)benzo[lmn] [3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone) supramolecular cages with different counter anions: ClO4- (2) and CF3SO3- (3) were constructed via subcomponent self-assembly to investigate both solvent and anion influences on their magnetic properties and compare them to cage 1 with a BF4- anion. Pyridyl-hydrazone bidentate ligand scaffolds were employed to replace the &apos;classical&apos; imidazole/thiazolyl-imine coordination units to induce SCO behaviour in these cages. 2 and 3 were structurally characterized by single-crystal X-ray diffraction analysis and electrospray ionization time-of-flight mass spectrometry. Magnetic susceptibilities of 1-3 and 1-3&lt;middle dot&gt;desolvated indicate that the solvents&apos; presence is in favor of the low-spin (LS) state. While different counter anions in 1-3&lt;middle dot&gt;desolvated affect the spin-state configurations of the four Fe-II metal centers. According to the Fe-57 M &amp; ouml;ssbauer spectral analysis, the spin-state distributions in 1-3 at 80 K are [2 high-spin (HS)-2LS], [1HS-3LS] and [2HS-2LS], respectively and density functional theory calculations were employed to investigate the reasons. These findings provide insights to regulate the spin-state versatility of SCO Fe-II cage systems in the solid state.

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

2024

Kód důvěrnosti údajů

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

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

53

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

12

Strana od-do

"1449–1459"

Kód UT WoS článku

001096351000001

EID výsledku v databázi Scopus

2-s2.0-85176119600