High pressure induced spin changes and magneto-structural correlations in hexametallic SMMs

Alessandro Prescimone, Constantinos J. Milios, Javier Sanchez-Benitez, Konstantin V. Kamenev, Claudia Loose, Jens Kortus, Stephen Moggach, Mark Murrie, John E. Warren, Alistair R. Lennie, Simon Parsons, Euan K. Brechin

Research output: Contribution to journalReview article

Abstract

The first combined high pressure single-crystal X-ray diffraction and high pressure magnetism study of two polymetallic clusters is presented in an attempt to correlate the observed changes in structure with changes in magnetic response without the need for changes in external ligation. At 1.5 GPa the structure of [Mn6O2(Et-sao)(6)(O2CPh(Me)(2))(2)(EtOH)(6)] (1; Et-saoH(2) = 2-hydroxyphenylpropanone)-a single molecule magnet (SMM) with an effective anisotropy barrier of similar to 86 K-and of [Mn6O2(Et-sao)(6)-(O2C- naphth)(2)(EtOH)(4)(H2O)(2)](2) both undergo significant structural distortions of their metallic skeletons, which has a direct effect upon the observed magnetic response. The application of hydrostatic pressure on the two compounds ( up to 1.5 GPa) flattens the Mn-N-O-Mn torsion angles weakening the magnetic exchange between the metal centres. In both compounds one interaction switches from ferro- to antiferromagnetic, with the Jahn-Teller (JT) axes compressing ( on average) and re-aligning differently with respect to the plane of the three metal centres. High pressure dc chi T-M plots display a gradual decrease in the low temperature peak height and slope, simulations showing a decrease in vertical bar J vertical bar with increasing pressure with a second antiferromagnetic J value required to simulate the data. The "ground states" change from S = 12 to S = 11 for 1 and to S = 10 for 2. Magnetisation data for both 1 and 2 suggest a small decrease in vertical bar D vertical bar, while out-of-phase (chi(M)'') ac data show a large decrease in the effective energy barrier for magnetisation reversal.

Original languageEnglish
Pages (from-to)4858-4867
Number of pages10
JournalDalton Transactions
Issue number25
DOIs
Publication statusPublished - 2009
Externally publishedYes

Cite this

Prescimone, A., Milios, C. J., Sanchez-Benitez, J., Kamenev, K. V., Loose, C., Kortus, J., ... Brechin, E. K. (2009). High pressure induced spin changes and magneto-structural correlations in hexametallic SMMs. Dalton Transactions, (25), 4858-4867. https://doi.org/10.1039/b902485a
Prescimone, Alessandro ; Milios, Constantinos J. ; Sanchez-Benitez, Javier ; Kamenev, Konstantin V. ; Loose, Claudia ; Kortus, Jens ; Moggach, Stephen ; Murrie, Mark ; Warren, John E. ; Lennie, Alistair R. ; Parsons, Simon ; Brechin, Euan K. / High pressure induced spin changes and magneto-structural correlations in hexametallic SMMs. In: Dalton Transactions. 2009 ; No. 25. pp. 4858-4867.
@article{217db71badac4474a7c9151bd9402904,
title = "High pressure induced spin changes and magneto-structural correlations in hexametallic SMMs",
abstract = "The first combined high pressure single-crystal X-ray diffraction and high pressure magnetism study of two polymetallic clusters is presented in an attempt to correlate the observed changes in structure with changes in magnetic response without the need for changes in external ligation. At 1.5 GPa the structure of [Mn6O2(Et-sao)(6)(O2CPh(Me)(2))(2)(EtOH)(6)] (1; Et-saoH(2) = 2-hydroxyphenylpropanone)-a single molecule magnet (SMM) with an effective anisotropy barrier of similar to 86 K-and of [Mn6O2(Et-sao)(6)-(O2C- naphth)(2)(EtOH)(4)(H2O)(2)](2) both undergo significant structural distortions of their metallic skeletons, which has a direct effect upon the observed magnetic response. The application of hydrostatic pressure on the two compounds ( up to 1.5 GPa) flattens the Mn-N-O-Mn torsion angles weakening the magnetic exchange between the metal centres. In both compounds one interaction switches from ferro- to antiferromagnetic, with the Jahn-Teller (JT) axes compressing ( on average) and re-aligning differently with respect to the plane of the three metal centres. High pressure dc chi T-M plots display a gradual decrease in the low temperature peak height and slope, simulations showing a decrease in vertical bar J vertical bar with increasing pressure with a second antiferromagnetic J value required to simulate the data. The {"}ground states{"} change from S = 12 to S = 11 for 1 and to S = 10 for 2. Magnetisation data for both 1 and 2 suggest a small decrease in vertical bar D vertical bar, while out-of-phase (chi(M)'') ac data show a large decrease in the effective energy barrier for magnetisation reversal.",
keywords = "TRANSITION-METAL-COMPLEXES, SINGLE-MOLECULE MAGNET, TARGETED STRUCTURAL DISTORTION, ZERO-FIELD SPLITTINGS, INELASTIC NEUTRON-SCATTERING, X-RAY-DIFFRACTION, CRYSTAL-STRUCTURE, DICOPPER(II) COMPLEXES, COPPER(II) COMPLEXES, MANGANESE COMPLEXES",
author = "Alessandro Prescimone and Milios, {Constantinos J.} and Javier Sanchez-Benitez and Kamenev, {Konstantin V.} and Claudia Loose and Jens Kortus and Stephen Moggach and Mark Murrie and Warren, {John E.} and Lennie, {Alistair R.} and Simon Parsons and Brechin, {Euan K.}",
year = "2009",
doi = "10.1039/b902485a",
language = "English",
pages = "4858--4867",
journal = "Dalton Transactions: the international journal for inorganic, organometallic and bioinorganic chemistry",
issn = "1477-9226",
publisher = "ROYAL SOC CHEMISTRY",
number = "25",

}

Prescimone, A, Milios, CJ, Sanchez-Benitez, J, Kamenev, KV, Loose, C, Kortus, J, Moggach, S, Murrie, M, Warren, JE, Lennie, AR, Parsons, S & Brechin, EK 2009, 'High pressure induced spin changes and magneto-structural correlations in hexametallic SMMs' Dalton Transactions, no. 25, pp. 4858-4867. https://doi.org/10.1039/b902485a

High pressure induced spin changes and magneto-structural correlations in hexametallic SMMs. / Prescimone, Alessandro; Milios, Constantinos J.; Sanchez-Benitez, Javier; Kamenev, Konstantin V.; Loose, Claudia; Kortus, Jens; Moggach, Stephen; Murrie, Mark; Warren, John E.; Lennie, Alistair R.; Parsons, Simon; Brechin, Euan K.

In: Dalton Transactions, No. 25, 2009, p. 4858-4867.

Research output: Contribution to journalReview article

TY - JOUR

T1 - High pressure induced spin changes and magneto-structural correlations in hexametallic SMMs

AU - Prescimone, Alessandro

AU - Milios, Constantinos J.

AU - Sanchez-Benitez, Javier

AU - Kamenev, Konstantin V.

AU - Loose, Claudia

AU - Kortus, Jens

AU - Moggach, Stephen

AU - Murrie, Mark

AU - Warren, John E.

AU - Lennie, Alistair R.

AU - Parsons, Simon

AU - Brechin, Euan K.

PY - 2009

Y1 - 2009

N2 - The first combined high pressure single-crystal X-ray diffraction and high pressure magnetism study of two polymetallic clusters is presented in an attempt to correlate the observed changes in structure with changes in magnetic response without the need for changes in external ligation. At 1.5 GPa the structure of [Mn6O2(Et-sao)(6)(O2CPh(Me)(2))(2)(EtOH)(6)] (1; Et-saoH(2) = 2-hydroxyphenylpropanone)-a single molecule magnet (SMM) with an effective anisotropy barrier of similar to 86 K-and of [Mn6O2(Et-sao)(6)-(O2C- naphth)(2)(EtOH)(4)(H2O)(2)](2) both undergo significant structural distortions of their metallic skeletons, which has a direct effect upon the observed magnetic response. The application of hydrostatic pressure on the two compounds ( up to 1.5 GPa) flattens the Mn-N-O-Mn torsion angles weakening the magnetic exchange between the metal centres. In both compounds one interaction switches from ferro- to antiferromagnetic, with the Jahn-Teller (JT) axes compressing ( on average) and re-aligning differently with respect to the plane of the three metal centres. High pressure dc chi T-M plots display a gradual decrease in the low temperature peak height and slope, simulations showing a decrease in vertical bar J vertical bar with increasing pressure with a second antiferromagnetic J value required to simulate the data. The "ground states" change from S = 12 to S = 11 for 1 and to S = 10 for 2. Magnetisation data for both 1 and 2 suggest a small decrease in vertical bar D vertical bar, while out-of-phase (chi(M)'') ac data show a large decrease in the effective energy barrier for magnetisation reversal.

AB - The first combined high pressure single-crystal X-ray diffraction and high pressure magnetism study of two polymetallic clusters is presented in an attempt to correlate the observed changes in structure with changes in magnetic response without the need for changes in external ligation. At 1.5 GPa the structure of [Mn6O2(Et-sao)(6)(O2CPh(Me)(2))(2)(EtOH)(6)] (1; Et-saoH(2) = 2-hydroxyphenylpropanone)-a single molecule magnet (SMM) with an effective anisotropy barrier of similar to 86 K-and of [Mn6O2(Et-sao)(6)-(O2C- naphth)(2)(EtOH)(4)(H2O)(2)](2) both undergo significant structural distortions of their metallic skeletons, which has a direct effect upon the observed magnetic response. The application of hydrostatic pressure on the two compounds ( up to 1.5 GPa) flattens the Mn-N-O-Mn torsion angles weakening the magnetic exchange between the metal centres. In both compounds one interaction switches from ferro- to antiferromagnetic, with the Jahn-Teller (JT) axes compressing ( on average) and re-aligning differently with respect to the plane of the three metal centres. High pressure dc chi T-M plots display a gradual decrease in the low temperature peak height and slope, simulations showing a decrease in vertical bar J vertical bar with increasing pressure with a second antiferromagnetic J value required to simulate the data. The "ground states" change from S = 12 to S = 11 for 1 and to S = 10 for 2. Magnetisation data for both 1 and 2 suggest a small decrease in vertical bar D vertical bar, while out-of-phase (chi(M)'') ac data show a large decrease in the effective energy barrier for magnetisation reversal.

KW - TRANSITION-METAL-COMPLEXES

KW - SINGLE-MOLECULE MAGNET

KW - TARGETED STRUCTURAL DISTORTION

KW - ZERO-FIELD SPLITTINGS

KW - INELASTIC NEUTRON-SCATTERING

KW - X-RAY-DIFFRACTION

KW - CRYSTAL-STRUCTURE

KW - DICOPPER(II) COMPLEXES

KW - COPPER(II) COMPLEXES

KW - MANGANESE COMPLEXES

U2 - 10.1039/b902485a

DO - 10.1039/b902485a

M3 - Review article

SP - 4858

EP - 4867

JO - Dalton Transactions: the international journal for inorganic, organometallic and bioinorganic chemistry

JF - Dalton Transactions: the international journal for inorganic, organometallic and bioinorganic chemistry

SN - 1477-9226

IS - 25

ER -

Prescimone A, Milios CJ, Sanchez-Benitez J, Kamenev KV, Loose C, Kortus J et al. High pressure induced spin changes and magneto-structural correlations in hexametallic SMMs. Dalton Transactions. 2009;(25):4858-4867. https://doi.org/10.1039/b902485a