Ferromagnetic exchange in a twisted, oxime-bridged [MnIII2] dimer

Edel Houton; Stephanie M. Taylor; Christopher C. Beedle; Joan Cano; Stergios Piligkos; Stephen Hill; Alan G. Ryder; Euan K. Brechin; Leigh F. Jones

doi:10.1039/c2dt30674c

Ferromagnetic exchange in a twisted, oxime-bridged [Mn^III₂] dimer

Edel Houton, Stephanie M. Taylor, Christopher C. Beedle, Joan Cano, Stergios Piligkos, Stephen Hill, Alan G. Ryder, Euan K. Brechin, Leigh F. Jones

Department of Chemistry

9 Citations (Scopus)

Abstract

The dimeric complex [Mn(III)(2)(Naphth-sao)(2)(Naphth-saoH)(2)(MeOH)(2)]·4MeOH (1·4MeOH), acts as a simple model complex with which to examine the magneto-structural relationship in polymetallic, oxime-bridged Mn(III) complexes. Dc magnetic susceptibility studies reveal that ferromagnetic exchange is mediated through the heavily twisted Mn-O-N-Mn moiety (J = +1.24 cm(-1)) with magnetisation measurements at low temperatures and high fields suggesting significant anisotropy. Simulations of high field, high frequency EPR data reveal a single ion anisotropy, D((Mn(III))) = -3.94 cm(-1). Theoretical studies on simplified model complexes of 1 reveal that calculated values of the exchange coupling and the anisotropy are in excellent agreement with experiment, with the weak ferromagnetism resulting from an accidental orthogonality between the Mn-N-O plane of the first Mn(III) ion and the Jahn-Teller axis of the second Mn(III) ion.

Original language	English
Journal	Dalton Transactions (Online)
Volume	41
Issue number	27
Pages (from-to)	8340-8347
Number of pages	8
ISSN	1477-9234
DOIs	https://doi.org/10.1039/c2dt30674c
Publication status	Published - 21 Jul 2012

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10.1039/c2dt30674c

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@article{aac784c33c9b43f69c8eb6db354bc45a,

title = "Ferromagnetic exchange in a twisted, oxime-bridged [MnIII2] dimer",

abstract = "The dimeric complex [Mn(III)(2)(Naphth-sao)(2)(Naphth-saoH)(2)(MeOH)(2)]·4MeOH (1·4MeOH), acts as a simple model complex with which to examine the magneto-structural relationship in polymetallic, oxime-bridged Mn(III) complexes. Dc magnetic susceptibility studies reveal that ferromagnetic exchange is mediated through the heavily twisted Mn-O-N-Mn moiety (J = +1.24 cm(-1)) with magnetisation measurements at low temperatures and high fields suggesting significant anisotropy. Simulations of high field, high frequency EPR data reveal a single ion anisotropy, D((Mn(III))) = -3.94 cm(-1). Theoretical studies on simplified model complexes of 1 reveal that calculated values of the exchange coupling and the anisotropy are in excellent agreement with experiment, with the weak ferromagnetism resulting from an accidental orthogonality between the Mn-N-O plane of the first Mn(III) ion and the Jahn-Teller axis of the second Mn(III) ion.",

author = "Edel Houton and Taylor, {Stephanie M.} and Beedle, {Christopher C.} and Joan Cano and Stergios Piligkos and Stephen Hill and Ryder, {Alan G.} and Brechin, {Euan K.} and Jones, {Leigh F.}",

year = "2012",

month = jul,

day = "21",

doi = "10.1039/c2dt30674c",

language = "English",

volume = "41",

pages = "8340--8347",

journal = "Dalton Transactions (Online)",

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publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Ferromagnetic exchange in a twisted, oxime-bridged [MnIII2] dimer

AU - Houton, Edel

AU - Taylor, Stephanie M.

AU - Beedle, Christopher C.

AU - Cano, Joan

AU - Piligkos, Stergios

AU - Hill, Stephen

AU - Ryder, Alan G.

AU - Brechin, Euan K.

AU - Jones, Leigh F.

PY - 2012/7/21

Y1 - 2012/7/21

N2 - The dimeric complex [Mn(III)(2)(Naphth-sao)(2)(Naphth-saoH)(2)(MeOH)(2)]·4MeOH (1·4MeOH), acts as a simple model complex with which to examine the magneto-structural relationship in polymetallic, oxime-bridged Mn(III) complexes. Dc magnetic susceptibility studies reveal that ferromagnetic exchange is mediated through the heavily twisted Mn-O-N-Mn moiety (J = +1.24 cm(-1)) with magnetisation measurements at low temperatures and high fields suggesting significant anisotropy. Simulations of high field, high frequency EPR data reveal a single ion anisotropy, D((Mn(III))) = -3.94 cm(-1). Theoretical studies on simplified model complexes of 1 reveal that calculated values of the exchange coupling and the anisotropy are in excellent agreement with experiment, with the weak ferromagnetism resulting from an accidental orthogonality between the Mn-N-O plane of the first Mn(III) ion and the Jahn-Teller axis of the second Mn(III) ion.

AB - The dimeric complex [Mn(III)(2)(Naphth-sao)(2)(Naphth-saoH)(2)(MeOH)(2)]·4MeOH (1·4MeOH), acts as a simple model complex with which to examine the magneto-structural relationship in polymetallic, oxime-bridged Mn(III) complexes. Dc magnetic susceptibility studies reveal that ferromagnetic exchange is mediated through the heavily twisted Mn-O-N-Mn moiety (J = +1.24 cm(-1)) with magnetisation measurements at low temperatures and high fields suggesting significant anisotropy. Simulations of high field, high frequency EPR data reveal a single ion anisotropy, D((Mn(III))) = -3.94 cm(-1). Theoretical studies on simplified model complexes of 1 reveal that calculated values of the exchange coupling and the anisotropy are in excellent agreement with experiment, with the weak ferromagnetism resulting from an accidental orthogonality between the Mn-N-O plane of the first Mn(III) ion and the Jahn-Teller axis of the second Mn(III) ion.

U2 - 10.1039/c2dt30674c

DO - 10.1039/c2dt30674c

M3 - Journal article

C2 - 22653157

SN - 1477-9234

VL - 41

SP - 8340

EP - 8347

JO - Dalton Transactions (Online)

JF - Dalton Transactions (Online)

IS - 27

ER -

Ferromagnetic exchange in a twisted, oxime-bridged [MnIII2] dimer

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Ferromagnetic exchange in a twisted, oxime-bridged [Mn^III₂] dimer