CER - Central Repository
Institute of Chemistry, Technology and Metallurgy
    • English
    • Српски
    • Српски (Serbia)
  • English 
    • English
    • Serbian (Cyrilic)
    • Serbian (Latin)
  • Login
View Item 
  •   Central Repository
  • IHTM
  • Radovi istraživača / Researchers' publications
  • View Item
  •   Central Repository
  • IHTM
  • Radovi istraživača / Researchers' publications
  • View Item
JavaScript is disabled for your browser. Some features of this site may not work without it.

Magnetic Anisotropy in "Scorpionate" First-Row Transition-Metal Complexes: A Theoretical Investigation

Thumbnail
2015
bitstream_7049.pdf (416.6Kb)
Authors
Perić, Marko
Garcia-Fuente, Amador
Zlatar, Matija
Daul, Claude
Stepanović, Stepan
Garcia-Fernandez, Pablo
Gruden-Pavlović, Maja
Article (Accepted Version)
Metadata
Show full item record
Abstract
In this work we have analyzed in detail the magnetic anisotropy in a series of hydrotris(pyrazolyl)borate (Tp(-)) metal complexes, namely [VTpCl](+), [CrTpCl](+), [MnTpCl](+), [FeTpCl], [CoTpCl], and [NiTpCl], and their substituted methyl and tert-butyl analogues with the goal of observing the effect of the ligand field on the magnetic properties. In the [VTpCl](+), [CrTpCl](+), [CoTpCl], and [NiTpCl] complexes, the magnetic anisotropy arises as a consequence of out-of-state spin-orbit coupling, and covalent changes induced by the substitution of hydrogen atoms on the pyrazolyl rings does not lead to drastic changes in the magnetic anisotropy. On the other hand, much larger magnetic anisotropies were predicted in complexes displaying a degenerate ground state, namely [MnTpCl](+) and [FeTpCl], due to in-state spin-orbit coupling. The anisotropy in these systems was shown to be very sensitive to perturbations, for example, chemical substitution and distortions due to the Jahn-Teller effe...ct. We found that by substituting the hydrogen atoms in [MnTpCl](+) and [FeTpCl] by methyl and tert-butyl groups, certain covalent contributions to the magnetic anisotropy energy (MAE) could be controlled, thereby achieving higher values. Moreover, we showed that the selection of ion has important consequences for the symmetry of the ground spin-orbit term, opening the possibility of achieving zero magnetic tunneling even in non-Kramers ions. We have also shown that substitution may also contribute to a quenching of the Jahn-Teller effect, which could significantly reduce the magnetic anisotropy of the complexes studied.

Keywords:
density functional calculations / Jahn-Teller distortion / ligand-field effects / magnetic properties / scorpionate complexes
Source:
Chemistry-A European Journal, 2015, 21, 9, 3716-3726
Publisher:
  • Wiley-VCH Verlag Gmbh, Weinheim
Projects:
  • Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-172035)
  • Swiss State Secretariat for Research and Innovation
  • Ramon y Cajal programme [RYC-2013-12515]
  • COST Action [CM1305, CM1006]
  • Spanish Ministerio of Economia y Competitividad [FIS2012-37549-C05-4]
  • Swiss National Science Foundation
Note:
  • This is peer-reviewed version of the article: https://10.1002/chem.201405480
  • http://cer.ihtm.bg.ac.rs/handle/123456789/1730

DOI: 10.1002/chem.201405480

ISSN: 0947-6539

PubMed: 25591004

WoS: 000350116200028

Scopus: 2-s2.0-84923044611
[ Google Scholar ]
12
12
URI
http://cer.ihtm.bg.ac.rs/handle/123456789/2911
Collections
  • Radovi istraživača / Researchers' publications
Institution
IHTM

DSpace software copyright © 2002-2015  DuraSpace
About CeR – Central Repository | Send Feedback

OpenAIRERCUB
 

 

All of DSpaceInstitutionsAuthorsTitlesSubjectsThis institutionAuthorsTitlesSubjects

Statistics

View Usage Statistics

DSpace software copyright © 2002-2015  DuraSpace
About CeR – Central Repository | Send Feedback

OpenAIRERCUB