Issue 28, 2024

Spin dynamics phenomena of a cerium(iii) double-decker complex induced by intramolecular electron transfer

Abstract

Switchable spin dynamic properties in single-molecule magnets (SMMs) via an applied stimulus have applications in single-molecule devices. Many SMMs containing heavy lanthanoid ions with strong uniaxial magnetic anisotropy have been reported to exhibit SMM characteristics in the absence of an external magnetic field. On the other hand, SMMs containing light lanthanoid cerium(III) (Ce3+) ions exhibit field-induced slow magnetic relaxation. We investigated the chemical conversion of a diamagnetic Ce4+ ion (4f0) to a paramagnetic Ce3+ ion (4f1) in Ce-phthalocyaninato double-decker complexes (TBA+[Ce(obPc)2] (1) and TBA+[Ce(Pc)2] (2)) which exhibit field-induced SMM behaviour due to a 4f1 system. The phthalocyaninato ligands with electron-donating substituents (obPc2− = 2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato) in 1 have a significant effect on the valence state of the Ce ion, which is reflected in its magnetic properties due to the mixed valence state of the Ce ion. Given that Ce double-decker complexes with π-conjugated ligands undergo intramolecular electron transfer (IET) to the Ce ion mixed valence state, characterised by a mixture of 4f0 and 4f1 configurations, we examined the dynamic disorder inherent in IET influencing magnetic relaxation.

Graphical abstract: Spin dynamics phenomena of a cerium(iii) double-decker complex induced by intramolecular electron transfer

Supplementary files

Article information

Article type
Paper
Submitted
15 Feb 2024
Accepted
17 Apr 2024
First published
18 Apr 2024
This article is Open Access
Creative Commons BY license

Dalton Trans., 2024,53, 11664-11677

Spin dynamics phenomena of a cerium(III) double-decker complex induced by intramolecular electron transfer

K. Kobayashi, M. Suzuki, T. Sato, Y. Horii, T. Yoshida, Brian. K. Breedlove, M. Yamashita and K. Katoh, Dalton Trans., 2024, 53, 11664 DOI: 10.1039/D4DT00436A

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