Late first-row transition metal complexes of a 17-membered piperazine-based macrocyclic ligand: structures and magnetism

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15310%2F20%3A73603262" target="_blank" >RIV/61989592:15310/20:73603262 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/20:10413888

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlehtml/2020/dt/d0dt01392g" target="_blank" >https://pubs.rsc.org/en/content/articlehtml/2020/dt/d0dt01392g</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d0dt01392g" target="_blank" >10.1039/d0dt01392g</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Late first-row transition metal complexes of a 17-membered piperazine-based macrocyclic ligand: structures and magnetism

Popis výsledku v původním jazyce

A 17-membered piperazine-based macrocyclic ligandL(diProp)(1,5,13,17,22-pentaazatricyclo[15.2.2.17,11]docosa-7,9,11(22)-triene) was resynthesized in high yield by using a linear pump. Its Mn(ii), Fe(ii), Co(ii) and Ni(ii) complexes of the general formula [MnLdiProp(ClO4)(2)] (1), [FeLdiProp(CH3CN)](ClO4)(2)(2), [CoLdiProp(CH3CN)](ClO4)(2)(3), [NiLdiProp](ClO4)(2)(4) were prepared and thoroughly characterized. X-ray diffraction analysis confirmed that Mn(ii) complex1has capped trigonal prismatic geometry with a coordination number of seven, Fe(ii) and Co(ii) complexes2and3are trigonal prismatic with a coordination number of six and Ni(ii) complex4has square pyramidal geometry with a coordination number of five. The decrease of the coordination number is accompanied by a shortening of M-N distances and an increase of torsion of the piperazine ring from the equatorial plane. Magnetic measurement reveals moderate anisotropy for4and rather large magnetic anisotropy for2and3(axial zero-field splitting parameterD(Ni) = 9.0 cm(-1),D(Fe) = -14.4 cm(-1),D(Co) = -25.8 cm(-1), together with rather high rhombicity). Co(ii) complex3behaves as a field-induced SMM with a combination of Raman and direct or Orbach and direct relaxation mechanisms. Obtained magnetic data were extensively supported by theoretical CASSCF calculations. The flexibility and rather large 17-membered macrocyclic cavity of ligandL(diProp)could be responsible for the variation of coordination numbers and geometries for the investigated late-first row transition metals.

Název v anglickém jazyce

Late first-row transition metal complexes of a 17-membered piperazine-based macrocyclic ligand: structures and magnetism

Popis výsledku anglicky

A 17-membered piperazine-based macrocyclic ligandL(diProp)(1,5,13,17,22-pentaazatricyclo[15.2.2.17,11]docosa-7,9,11(22)-triene) was resynthesized in high yield by using a linear pump. Its Mn(ii), Fe(ii), Co(ii) and Ni(ii) complexes of the general formula [MnLdiProp(ClO4)(2)] (1), [FeLdiProp(CH3CN)](ClO4)(2)(2), [CoLdiProp(CH3CN)](ClO4)(2)(3), [NiLdiProp](ClO4)(2)(4) were prepared and thoroughly characterized. X-ray diffraction analysis confirmed that Mn(ii) complex1has capped trigonal prismatic geometry with a coordination number of seven, Fe(ii) and Co(ii) complexes2and3are trigonal prismatic with a coordination number of six and Ni(ii) complex4has square pyramidal geometry with a coordination number of five. The decrease of the coordination number is accompanied by a shortening of M-N distances and an increase of torsion of the piperazine ring from the equatorial plane. Magnetic measurement reveals moderate anisotropy for4and rather large magnetic anisotropy for2and3(axial zero-field splitting parameterD(Ni) = 9.0 cm(-1),D(Fe) = -14.4 cm(-1),D(Co) = -25.8 cm(-1), together with rather high rhombicity). Co(ii) complex3behaves as a field-induced SMM with a combination of Raman and direct or Orbach and direct relaxation mechanisms. Obtained magnetic data were extensively supported by theoretical CASSCF calculations. The flexibility and rather large 17-membered macrocyclic cavity of ligandL(diProp)could be responsible for the variation of coordination numbers and geometries for the investigated late-first row transition metals.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

S - Specificky vyzkum na vysokych skolach

Rok uplatnění

2020

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

—

Svazek periodika

49

Číslo periodika v rámci svazku

26

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

13

Strana od-do

9057-9069

Kód UT WoS článku

000552458700025

EID výsledku v databázi Scopus

2-s2.0-85088042098