Publication detail

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

ZAHRADNÍKOVÁ, E. HERCHEL, R. ŠALITROŠ, I. CÍSAŘOVÁ, I. DRAHOŠ, B.

Original Title

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

Type

journal article in Web of Science

Language

English

Original Abstract

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.

Keywords

STATE PERTURBATION-THEORY; SINGLE-ION MAGNET; BASIS-SETS; VALENCE; ANISOTROPY; RELAXATION; CRYSTAL; PYRIDINE; IMPLEMENTATION; VISUALIZATION

Authors

ZAHRADNÍKOVÁ, E.; HERCHEL, R.; ŠALITROŠ, I.; CÍSAŘOVÁ, I.; DRAHOŠ, B.

Released

14. 7. 2020

Publisher

ROYAL SOC CHEMISTRY

Location

CAMBRIDGE

ISBN

1477-9234

Periodical

Dalton Transactions

Year of study

49

Number

26

State

United Kingdom of Great Britain and Northern Ireland

Pages from

9057

Pages to

9069

Pages count

13

URL

https://pubs.rsc.org/en/content/articlehtml/2020/dt/d0dt01392g

BibTex

@article{BUT165520,
  author="Eva {Zahradníková} and Radovan {Herchel} and Ivan {Šalitroš} and Ivana {Císařová} and Bohuslav {Drahoš}",
  title="Late first-row transition metal complexes of a 17-membered piperazine-based macrocyclic ligand: structures and magnetism",
  journal="Dalton Transactions",
  year="2020",
  volume="49",
  number="26",
  pages="9057--9069",
  doi="10.1039/d0dt01392g",
  issn="1477-9234",
  url="https://pubs.rsc.org/en/content/articlehtml/2020/dt/d0dt01392g"
}