Please use this identifier to cite or link to this item: https://doi.org/10.1039/c2sc20649h
Title: Hysteresis in the ground and excited spin state up to 10 T of a [(Mn6MnIII)-Mn-III](3+) triplesalen single-molecule magnet
Authors: Hoeke, Veronika
Gieb, Klaus
Mueller, Paul
Ungur, Liviu 
Chibotaru, Liviu F
Heidemeier, Maik
Krickemeyer, Erich
Stammler, Anja
Boegge, Hartmut
Schroeder, Christian
Schnack, Juergen
Glaser, Thorsten
Keywords: Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
POLARIZATION MECHANISM
QUANTUM COMPUTERS
CYANIDE CLUSTER
COMPLEXES
BEHAVIOR
MAGNETIZATION
EXCHANGE
LIGANDS
BARRIER
FERRIMAGNETS
Issue Date: 1-Jan-2012
Publisher: ROYAL SOC CHEMISTRY
Citation: Hoeke, Veronika, Gieb, Klaus, Mueller, Paul, Ungur, Liviu, Chibotaru, Liviu F, Heidemeier, Maik, Krickemeyer, Erich, Stammler, Anja, Boegge, Hartmut, Schroeder, Christian, Schnack, Juergen, Glaser, Thorsten (2012-01-01). Hysteresis in the ground and excited spin state up to 10 T of a [(Mn6MnIII)-Mn-III](3+) triplesalen single-molecule magnet. CHEMICAL SCIENCE 3 (9) : 2868-2882. ScholarBank@NUS Repository. https://doi.org/10.1039/c2sc20649h
Abstract: We have synthesized the triplesalen-based single-molecule magnet (SMM) [Mn III6Mn III] 3+ as a variation of our SMM [Mn III6Cr III](BPh 4) 3. The use of the rod-shaped anion lactate (lac) was intended to enforce a rod packing and resulted in the crystallization of [Mn III6Mn III](lac) 3 in the highly symmetric space group R3. This entails a crystallographic S 6 symmetry of the [Mn III6Mn III] 3+ molecules, which in addition are all aligned with the crystallographic c axis. Moreover, the molecular environment of each [Mn III6Mn III] 3+ molecule is highly symmetric. Single-crystals of [Mn III6Mn III](lac) 3 exhibit a double hysteresis at 0.3 K with a hysteretic opening not only for the spin ground state up to 1.8 T, but also for an excited state becoming the ground state at ≈ 3.4 T with a hysteretic opening up to 10 T. Ab initio calculations including spin-orbit coupling establish a non-magnetic behavior of the central Mn III low-spin (l.s.) ion at low temperatures, demonstrating that predictions from ligand-field theory are corroborated in the case of Mn III l.s. by ab intio calculations. Simulations of the field- and temperature-dependent magnetization data indicate that [Mn III6Mn III] 3+ is in the limit of weak exchange (J ≪ D) with antiferromagnetic interactions in the trinuclear Mn III3 triplesalen subunits resulting in intermediate S* = 2 spins. Slight ferromagnetic interactions between the two trinuclear Mn III3 subunits lead to a ground state in zero-field that is approximately described by a total spin quantum number S = 4. This ground state exhibits only a very small anisotropy barrier due to the misalignment of the local zero-field splitting tensors. At higher magnetic fields of ≈ 3.4 T, the spin configuration changes to an all-up orientation of the local Mn III spins, with the main part of the Zeeman energy needed for the spin-flip being required to overcome the local Mn III anisotropy barriers, while only minor contributions of the Zeeman energy are needed to overcome the antiferromagnetic interactions. These combined theoretical analyses provide a clear picture of the double-hysteretic behavior of the [Mn III6Mn III] 3+ single-molecule magnet with hysteretic openings up to 10 T. © 2012 The Royal Society of Chemistry.
Source Title: CHEMICAL SCIENCE
URI: https://scholarbank.nus.edu.sg/handle/10635/228789
ISSN: 20416520
20416539
DOI: 10.1039/c2sc20649h
Appears in Collections:Staff Publications
Elements

Show full item record
Files in This Item:
File Description SizeFormatAccess SettingsVersion 
Habib_CS_2012.pdfPublished version572.6 kBAdobe PDF

CLOSED

None
Hoeke_CS_2012.cif.txtSupporting information39.81 kBText

CLOSED

None
Hoeke_CS_2012_SI.pdfSupporting information767.14 kBAdobe PDF

CLOSED

None
Hoeke_CS_2012_movie_1.aviSupporting information742.23 kBAVI

CLOSED

None
Hoeke_CS_2012_movie_3.aviSupporting information874.44 kBAVI

CLOSED

None
Hoeke_CS_2012_movie_2.aviSupporting information2.19 MBAVI

CLOSED

None
Hoeke_CS_2012_movie_4.aviSupporting information2.19 MBAVI

CLOSED

None

SCOPUSTM   
Citations

34
checked on Nov 25, 2022

Page view(s)

43
checked on Nov 17, 2022

Download(s)

1
checked on Nov 17, 2022

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.