First step in preparation of multifunctional spin crossover material based on Fe(II) complex of cyclam-based ligand. Magnetism and DFT studies

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F19%3A73598090" target="_blank" >RIV/61989592:15310/19:73598090 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/pii/S0020169319302488" target="_blank" >https://www.sciencedirect.com/science/article/pii/S0020169319302488</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.ica.2019.05.020" target="_blank" >10.1016/j.ica.2019.05.020</a>

Jazyk výsledku

angličtina

Název v původním jazyce

First step in preparation of multifunctional spin crossover material based on Fe(II) complex of cyclam-based ligand. Magnetism and DFT studies

Popis výsledku v původním jazyce

With the aim to make the first step in preparation of magnetic multifunctional material combining spin crossover (SCO) together with single-molecule magnet (SMM) properties in one molecule (polynuclear complex), a specially designed ligand L-NH2 (1,8-bis(4-aminobenzyl)-4,11-bis(pyridin-2-ylmethyl)-1,4,8,11-tetra-azacyclotetradecane) was synthesized. It contains (i) macrocyclic cyclam core substituted with two 2-pyridylmethyl pendant arms suitable for complexation of Fe(II), because such system was previously proven to provide SCO, and (ii) two p-aminobenzyl pendant arms introducing NH2 groups suitable for consequent attachment of SMM molecule (e.g. transformation to functional groups for selective complexation of other metals). Furthermore, Fe(II) complex [Fe(L-NH2)]Cl-2 center dot 2.5H(2)O was prepared and characterized. Unfortunately, according to the magnetic measurements, SCO behavior was not observed and the complex remained in high-spin state with relatively high magnetic anisotropy (D = -17.7 cm(-1), E/D = 0.31). This magnetic behavior was rationalized by the DFT computational study, which identified high-spin state as preferential for prepared complex in contrast to other structurally similar SCO systems with low-spin state preference. The most probable reason behind this difference appeared to be the electron-withdrawing effect of benzyl groups providing weaker ligand field of macrocyclic nitrogen donor atoms.

Název v anglickém jazyce

First step in preparation of multifunctional spin crossover material based on Fe(II) complex of cyclam-based ligand. Magnetism and DFT studies

Popis výsledku anglicky

With the aim to make the first step in preparation of magnetic multifunctional material combining spin crossover (SCO) together with single-molecule magnet (SMM) properties in one molecule (polynuclear complex), a specially designed ligand L-NH2 (1,8-bis(4-aminobenzyl)-4,11-bis(pyridin-2-ylmethyl)-1,4,8,11-tetra-azacyclotetradecane) was synthesized. It contains (i) macrocyclic cyclam core substituted with two 2-pyridylmethyl pendant arms suitable for complexation of Fe(II), because such system was previously proven to provide SCO, and (ii) two p-aminobenzyl pendant arms introducing NH2 groups suitable for consequent attachment of SMM molecule (e.g. transformation to functional groups for selective complexation of other metals). Furthermore, Fe(II) complex [Fe(L-NH2)]Cl-2 center dot 2.5H(2)O was prepared and characterized. Unfortunately, according to the magnetic measurements, SCO behavior was not observed and the complex remained in high-spin state with relatively high magnetic anisotropy (D = -17.7 cm(-1), E/D = 0.31). This magnetic behavior was rationalized by the DFT computational study, which identified high-spin state as preferential for prepared complex in contrast to other structurally similar SCO systems with low-spin state preference. The most probable reason behind this difference appeared to be the electron-withdrawing effect of benzyl groups providing weaker ligand field of macrocyclic nitrogen donor atoms.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA17-08992S" target="_blank" >GA17-08992S: Magneticky multifunkční molekulové materiály</a><br>

Návaznosti

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

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

INORGANICA CHIMICA ACTA

ISSN

0020-1693

e-ISSN

—

Svazek periodika

495

Číslo periodika v rámci svazku

SEP

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

7

Strana od-do

"118921-1"-"118921-7"

Kód UT WoS článku

000481728800002

EID výsledku v databázi Scopus

2-s2.0-85067232926