Publication detail

Pentacoordinate cobalt(ii) single ion magnets with pendant alkyl chains: shall we go for chloride or bromide?

JURÁKOVÁ, J. DUBNICKÁ MIDLÍKOVÁ, J. HRUBÝ, J. KLIUIKOV, A. SANTANA, V. PAVLIK, J. MONCOL, J. MOHELSKY, I. ORLITA, M. NEUGEBAUER, P. GENTILI, D. CAVALLINI, M. ŠALITROŠ, I.

Original Title

Pentacoordinate cobalt(ii) single ion magnets with pendant alkyl chains: shall we go for chloride or bromide?

Type

journal article in Web of Science

Language

English

Original Abstract

Four pentacoordinate complexes, 1–4, of the type [Co(L1)X2] and [Co(L2)X2] (where L1 = 2,6-bis(1-octyl-1H-benzimidazol-2-yl)pyridine for 1 and 2, L2 = 2,6-bis(1-dodecyl-1H-benzimidazol-2-yl)-pyridine for 3 and 4; X = Cl− for 1 and 3, X = Br− for 2 and 4) have been synthesized, and their structures have been determined by X-ray analysis. The DC magnetic investigation confirmed the high-spin and anisotropic behavior of the metal centers of the reported compounds, and magnetic data were analyzed with respect to the spin Hamiltonian and the Griffith–Figgis Hamiltonian. CASSCF-NEVPT2 analysis enabled us to identify triaxial magnetic anisotropy for 1 and 2 and axial anisotropy for 3 and 4, and we discuss thoroughly the relationship between geometry and orbital ordering. The g-tensor components of the ground Kramers doublet extracted from EPR spectroscopy are compatible with this prediction of magnetic anisotropy. Simulated FIRMS experimental data of 2, 3 and 4 show very good agreement with theoretical calculations and provide precise values of zero-field splitting. The AC susceptibility measurements confirmed that the reported complexes were field-induced single-ion magnets. The slow relaxation of magnetization in 1 and 2 is mediated through two relaxation channels that are unusually close to each other. On the other hand, complexes 3 and 4 show the single-channel relaxation of magnetization, and their isostructural characteristic allowed us to study the relaxation changes caused solely by the replacement of terminal halido ligands. Finally, a wet lithographic technique has been used to evaluate both the processability of the complexes in solution and the preparation of microstructured films.

Keywords

TRANSITION MOLECULAR MATERIALS; SMMS; MAGNETOCHEMISTRY; SOLID-STATE; COBALT(II) COMPLEX; EPR;

Authors

JURÁKOVÁ, J.; DUBNICKÁ MIDLÍKOVÁ, J.; HRUBÝ, J.; KLIUIKOV, A.; SANTANA, V.; PAVLIK, J.; MONCOL, J.; MOHELSKY, I.; ORLITA, M.; NEUGEBAUER, P.; GENTILI, D.; CAVALLINI, M.; ŠALITROŠ, I.

Released

14. 1. 2022

Publisher

ROYAL SOC CHEMISTRY

Location

CAMBRIDGE

ISBN

2052-1553

Periodical

Inorganic Chemistry Frontiers

Year of study

9

Number

6

State

United Kingdom of Great Britain and Northern Ireland

Pages from

1179

Pages to

1194

Pages count

16

URL

http://dx.doi.org/10.1039/D1QI01350E

BibTex

@article{BUT176502,
  author="JURÁKOVÁ, J. and DUBNICKÁ MIDLÍKOVÁ, J. and HRUBÝ, J. and KLIUIKOV, A. and SANTANA, V. and PAVLIK, J. and MONCOL, J. and MOHELSKY, I. and ORLITA, M. and NEUGEBAUER, P. and GENTILI, D. and CAVALLINI, M. and ŠALITROŠ, I.",
  title="Pentacoordinate cobalt(ii) single ion magnets with pendant alkyl chains: shall we go for chloride or bromide?",
  journal="Inorganic Chemistry Frontiers",
  year="2022",
  volume="9",
  number="6",
  pages="1179--1194",
  doi="10.1039/D1QI01350E",
  issn="2052-1553",
  url="http://dx.doi.org/10.1039/D1QI01350E"
}