Magnetic properties of a family of [MnIII4LnIII4] wheel complexes: an experimental and theoretical study

Gavin A. Craig, Gunasekaran Velmurugan, Claire Wilson, Rafael Valiente, Gopalan Rajaraman, Mark Murrie

Research output: Contribution to journalArticle

Abstract

The chelating ligand 1,3-bis(tris(hydroxymethyl)methylamino)propane (H6L) has been used to synthesize a family of octanuclear heterometallic complexes with the formula (NMe4)3[Mn4Ln4(H2L)3(H3L)(NO3)12] (Ln = La (1), Ce (2), Pr (3), Nd (4)). Encapsulation by the ligand causes the Mn(III) centers to lie in an unusually distorted (∼C2v) environment, which is shown by density functional theory and complete active space self-consistent field calculations to impact on the magnetic anisotropy of the Mn(III) ion. The theoretical study also supports the experimental observation of a ferromagnetic superexchange interaction between the Mn(III) ions in 1, despite the ions being separated by the diamagnetic La(III) ion. The optical properties of the compounds show that the distortion of the Mn(III) ions leads to three broad absorption bands originating from the transition metal ion, while the Nd(III) containing complex also displays some weak sharp features arising from the lanthanide f–f transitions.
LanguageEnglish
Pages13815-13825
Number of pages11
JournalInorganic Chemistry
Volume58
Issue number20
Early online date7 Oct 2019
DOIs
Publication statusPublished - 21 Oct 2019

Fingerprint

wheels
Magnetic properties
Wheels
Ions
magnetic properties
ions
Ligands
Lanthanoid Series Elements
ligands
Magnetic anisotropy
Chelation
Encapsulation
propane
Transition metals
Density functional theory
Metal ions
self consistent fields
Absorption spectra
metal ions
Optical properties

Keywords

  • chelating ligands
  • octanuclear heterometallic complexes
  • nanomagnets

Cite this

Craig, Gavin A. ; Velmurugan, Gunasekaran ; Wilson, Claire ; Valiente, Rafael ; Rajaraman, Gopalan ; Murrie, Mark. / Magnetic properties of a family of [MnIII4LnIII4] wheel complexes : an experimental and theoretical study. In: Inorganic Chemistry. 2019 ; Vol. 58, No. 20. pp. 13815-13825.
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abstract = "The chelating ligand 1,3-bis(tris(hydroxymethyl)methylamino)propane (H6L) has been used to synthesize a family of octanuclear heterometallic complexes with the formula (NMe4)3[Mn4Ln4(H2L)3(H3L)(NO3)12] (Ln = La (1), Ce (2), Pr (3), Nd (4)). Encapsulation by the ligand causes the Mn(III) centers to lie in an unusually distorted (∼C2v) environment, which is shown by density functional theory and complete active space self-consistent field calculations to impact on the magnetic anisotropy of the Mn(III) ion. The theoretical study also supports the experimental observation of a ferromagnetic superexchange interaction between the Mn(III) ions in 1, despite the ions being separated by the diamagnetic La(III) ion. The optical properties of the compounds show that the distortion of the Mn(III) ions leads to three broad absorption bands originating from the transition metal ion, while the Nd(III) containing complex also displays some weak sharp features arising from the lanthanide f–f transitions.",
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Magnetic properties of a family of [MnIII4LnIII4] wheel complexes : an experimental and theoretical study. / Craig, Gavin A.; Velmurugan, Gunasekaran; Wilson, Claire; Valiente, Rafael; Rajaraman, Gopalan; Murrie, Mark.

In: Inorganic Chemistry, Vol. 58, No. 20, 21.10.2019, p. 13815-13825.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Magnetic properties of a family of [MnIII4LnIII4] wheel complexes

T2 - Inorganic Chemistry

AU - Craig, Gavin A.

AU - Velmurugan, Gunasekaran

AU - Wilson, Claire

AU - Valiente, Rafael

AU - Rajaraman, Gopalan

AU - Murrie, Mark

PY - 2019/10/21

Y1 - 2019/10/21

N2 - The chelating ligand 1,3-bis(tris(hydroxymethyl)methylamino)propane (H6L) has been used to synthesize a family of octanuclear heterometallic complexes with the formula (NMe4)3[Mn4Ln4(H2L)3(H3L)(NO3)12] (Ln = La (1), Ce (2), Pr (3), Nd (4)). Encapsulation by the ligand causes the Mn(III) centers to lie in an unusually distorted (∼C2v) environment, which is shown by density functional theory and complete active space self-consistent field calculations to impact on the magnetic anisotropy of the Mn(III) ion. The theoretical study also supports the experimental observation of a ferromagnetic superexchange interaction between the Mn(III) ions in 1, despite the ions being separated by the diamagnetic La(III) ion. The optical properties of the compounds show that the distortion of the Mn(III) ions leads to three broad absorption bands originating from the transition metal ion, while the Nd(III) containing complex also displays some weak sharp features arising from the lanthanide f–f transitions.

AB - The chelating ligand 1,3-bis(tris(hydroxymethyl)methylamino)propane (H6L) has been used to synthesize a family of octanuclear heterometallic complexes with the formula (NMe4)3[Mn4Ln4(H2L)3(H3L)(NO3)12] (Ln = La (1), Ce (2), Pr (3), Nd (4)). Encapsulation by the ligand causes the Mn(III) centers to lie in an unusually distorted (∼C2v) environment, which is shown by density functional theory and complete active space self-consistent field calculations to impact on the magnetic anisotropy of the Mn(III) ion. The theoretical study also supports the experimental observation of a ferromagnetic superexchange interaction between the Mn(III) ions in 1, despite the ions being separated by the diamagnetic La(III) ion. The optical properties of the compounds show that the distortion of the Mn(III) ions leads to three broad absorption bands originating from the transition metal ion, while the Nd(III) containing complex also displays some weak sharp features arising from the lanthanide f–f transitions.

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KW - nanomagnets

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