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Magnetic anisotropy in trigonal planar Fe(ii) bis(trimethylsilyl)amido complexes of the type [Fe{N(SiMe₃)₂}₂L]—experiment and theory

Bodenstein, Tilmann 1; Eichhöfer, Andreas 1
1 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)


Systematic ac (alternating current) magnetic investigations on four new trigonal planar high-spin Fe2+ complexes [Fe{N(SiMe3)2}2L] reveal that complexes which comprise a phosphine or arsine type ligand (L =PPh3, PMe3 and AsPh3) display slow magnetic relaxation at temperatures below 8 K under applied dc(direct current) fields, whereas a complex with a phosphine oxide ligand (L = OPPh3) does not. Accordingly, the parameters characteristic for magnetic anisotropy, derived both from dc magnetic measurements and quantum chemical calculations, reveal distinct differences for these two types of complexes. Extensive ab initio calculations of multi-reference wave function type were performed on the four new complexes listed above and the related reported ones with L = py, thf and PCy3 in order to get a reasonable description of the local electronic states involved in the magnetic relaxation. These calculations confirm that strong spin–orbit effects generate the magnetic anisotropy of complexes with L = PPh3, PMe3, AsPh3 and PCy3. On the other hand, the complexes with L = OPPh3, py and THF exhibit only small spin–orbit splittings, consistent with the fast relaxation found experimentally.

Verlagsausgabe §
DOI: 10.5445/IR/1000098883
Veröffentlicht am 16.10.2019
DOI: 10.1039/c9dt01702j
Zitationen: 12
Web of Science
Zitationen: 12
Zitationen: 12
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2019
Sprache Englisch
Identifikator ISSN: 1477-9226, 1477-9234
KITopen-ID: 1000098883
HGF-Programm 43.21.04 (POF III, LK 01) Molecular Engineering
Erschienen in Dalton transactions
Verlag Royal Society of Chemistry (RSC)
Band 48
Seiten 15699-15712
Vorab online veröffentlicht am 20.09.2019
Nachgewiesen in Scopus
Web of Science
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