Probing the origin of the giant magnetic anisotropy in trigonal bipyramidal Ni(ii) under high pressure

Gavin A. Craig, Arup Sarkar, Christopher H. Woodall, Moya A. Hay, Katie E. R. Marriott, Konstantin V. Kamenev, Stephen A. Moggach, Euan K. Brechin, Simon Parsons, Gopalan Rajaraman, Mark Murrie

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Understanding and controlling magnetic anisotropy at the level of a single metal ion is vital if the miniaturisation of data storage is to continue to evolve into transformative technologies. Magnetic anisotropy is essential for a molecule-based magnetic memory as it pins the magnetic moment of a metal ion along the easy axis. Devices will require deposition of magnetic molecules on surfaces, where changes in molecular structure can significantly alter magnetic properties. Furthermore, if we are to use coordination complexes with high magnetic anisotropy as building blocks for larger systems we need to know how magnetic anisotropy is affected by structural distortions. Here we study a trigonal bipyramidal nickel(ii) complex where a giant magnetic anisotropy of several hundred wavenumbers can be engineered. By using high pressure, we show how the magnetic anisotropy is strongly influenced by small structural distortions. Using a combination of high pressure X-ray diffraction, ab initio methods and high pressure magnetic measurements, we find that hydrostatic pressure lowers both the trigonal symmetry and axial anisotropy, while increasing the rhombic anisotropy. The ligand–metal–ligand angles in the equatorial plane are found to play a crucial role in tuning the energy separation between the dx2−y2 and dxy orbitals, which is the determining factor that controls the magnitude of the axial anisotropy. These results demonstrate that the combination of high pressure techniques with ab initio studies is a powerful tool that gives a unique insight into the design of systems that show giant magnetic anisotropy.
LanguageEnglish
Pages1551-1559
Number of pages9
JournalChemical Science
Volume9
Issue number6
DOIs
Publication statusPublished - 19 Dec 2017

Fingerprint

Magnetic anisotropy
Anisotropy
Metal ions
Ligands
Data storage equipment
Molecules
Coordination Complexes
Magnetic variables measurement
Hydrostatic pressure
Pressure measurement
Nickel
Magnetic moments
Molecular structure
Magnetic properties
Tuning
Metals
X ray diffraction

Keywords

  • magnetic anisotropy
  • trigonal bipyramidal Ni(II)
  • high pressure
  • X-ray diffraction

Cite this

Craig, G. A., Sarkar, A., Woodall, C. H., Hay, M. A., Marriott, K. E. R., Kamenev, K. V., ... Murrie, M. (2017). Probing the origin of the giant magnetic anisotropy in trigonal bipyramidal Ni(ii) under high pressure. Chemical Science, 9(6), 1551-1559. https://doi.org/10.1039/C7SC04460G
Craig, Gavin A. ; Sarkar, Arup ; Woodall, Christopher H. ; Hay, Moya A. ; Marriott, Katie E. R. ; Kamenev, Konstantin V. ; Moggach, Stephen A. ; Brechin, Euan K. ; Parsons, Simon ; Rajaraman, Gopalan ; Murrie, Mark. / Probing the origin of the giant magnetic anisotropy in trigonal bipyramidal Ni(ii) under high pressure. In: Chemical Science. 2017 ; Vol. 9, No. 6. pp. 1551-1559.
@article{cc6a71dadb1e434ebebd7b43350f8c23,
title = "Probing the origin of the giant magnetic anisotropy in trigonal bipyramidal Ni(ii) under high pressure",
abstract = "Understanding and controlling magnetic anisotropy at the level of a single metal ion is vital if the miniaturisation of data storage is to continue to evolve into transformative technologies. Magnetic anisotropy is essential for a molecule-based magnetic memory as it pins the magnetic moment of a metal ion along the easy axis. Devices will require deposition of magnetic molecules on surfaces, where changes in molecular structure can significantly alter magnetic properties. Furthermore, if we are to use coordination complexes with high magnetic anisotropy as building blocks for larger systems we need to know how magnetic anisotropy is affected by structural distortions. Here we study a trigonal bipyramidal nickel(ii) complex where a giant magnetic anisotropy of several hundred wavenumbers can be engineered. By using high pressure, we show how the magnetic anisotropy is strongly influenced by small structural distortions. Using a combination of high pressure X-ray diffraction, ab initio methods and high pressure magnetic measurements, we find that hydrostatic pressure lowers both the trigonal symmetry and axial anisotropy, while increasing the rhombic anisotropy. The ligand–metal–ligand angles in the equatorial plane are found to play a crucial role in tuning the energy separation between the dx2−y2 and dxy orbitals, which is the determining factor that controls the magnitude of the axial anisotropy. These results demonstrate that the combination of high pressure techniques with ab initio studies is a powerful tool that gives a unique insight into the design of systems that show giant magnetic anisotropy.",
keywords = "magnetic anisotropy, trigonal bipyramidal Ni(II), high pressure, X-ray diffraction",
author = "Craig, {Gavin A.} and Arup Sarkar and Woodall, {Christopher H.} and Hay, {Moya A.} and Marriott, {Katie E. R.} and Kamenev, {Konstantin V.} and Moggach, {Stephen A.} and Brechin, {Euan K.} and Simon Parsons and Gopalan Rajaraman and Mark Murrie",
year = "2017",
month = "12",
day = "19",
doi = "10.1039/C7SC04460G",
language = "English",
volume = "9",
pages = "1551--1559",
journal = "Chemical Science",
issn = "2041-6520",
number = "6",

}

Craig, GA, Sarkar, A, Woodall, CH, Hay, MA, Marriott, KER, Kamenev, KV, Moggach, SA, Brechin, EK, Parsons, S, Rajaraman, G & Murrie, M 2017, 'Probing the origin of the giant magnetic anisotropy in trigonal bipyramidal Ni(ii) under high pressure' Chemical Science, vol. 9, no. 6, pp. 1551-1559. https://doi.org/10.1039/C7SC04460G

Probing the origin of the giant magnetic anisotropy in trigonal bipyramidal Ni(ii) under high pressure. / Craig, Gavin A.; Sarkar, Arup; Woodall, Christopher H.; Hay, Moya A.; Marriott, Katie E. R.; Kamenev, Konstantin V.; Moggach, Stephen A.; Brechin, Euan K.; Parsons, Simon; Rajaraman, Gopalan; Murrie, Mark.

In: Chemical Science, Vol. 9, No. 6, 19.12.2017, p. 1551-1559.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Probing the origin of the giant magnetic anisotropy in trigonal bipyramidal Ni(ii) under high pressure

AU - Craig, Gavin A.

AU - Sarkar, Arup

AU - Woodall, Christopher H.

AU - Hay, Moya A.

AU - Marriott, Katie E. R.

AU - Kamenev, Konstantin V.

AU - Moggach, Stephen A.

AU - Brechin, Euan K.

AU - Parsons, Simon

AU - Rajaraman, Gopalan

AU - Murrie, Mark

PY - 2017/12/19

Y1 - 2017/12/19

N2 - Understanding and controlling magnetic anisotropy at the level of a single metal ion is vital if the miniaturisation of data storage is to continue to evolve into transformative technologies. Magnetic anisotropy is essential for a molecule-based magnetic memory as it pins the magnetic moment of a metal ion along the easy axis. Devices will require deposition of magnetic molecules on surfaces, where changes in molecular structure can significantly alter magnetic properties. Furthermore, if we are to use coordination complexes with high magnetic anisotropy as building blocks for larger systems we need to know how magnetic anisotropy is affected by structural distortions. Here we study a trigonal bipyramidal nickel(ii) complex where a giant magnetic anisotropy of several hundred wavenumbers can be engineered. By using high pressure, we show how the magnetic anisotropy is strongly influenced by small structural distortions. Using a combination of high pressure X-ray diffraction, ab initio methods and high pressure magnetic measurements, we find that hydrostatic pressure lowers both the trigonal symmetry and axial anisotropy, while increasing the rhombic anisotropy. The ligand–metal–ligand angles in the equatorial plane are found to play a crucial role in tuning the energy separation between the dx2−y2 and dxy orbitals, which is the determining factor that controls the magnitude of the axial anisotropy. These results demonstrate that the combination of high pressure techniques with ab initio studies is a powerful tool that gives a unique insight into the design of systems that show giant magnetic anisotropy.

AB - Understanding and controlling magnetic anisotropy at the level of a single metal ion is vital if the miniaturisation of data storage is to continue to evolve into transformative technologies. Magnetic anisotropy is essential for a molecule-based magnetic memory as it pins the magnetic moment of a metal ion along the easy axis. Devices will require deposition of magnetic molecules on surfaces, where changes in molecular structure can significantly alter magnetic properties. Furthermore, if we are to use coordination complexes with high magnetic anisotropy as building blocks for larger systems we need to know how magnetic anisotropy is affected by structural distortions. Here we study a trigonal bipyramidal nickel(ii) complex where a giant magnetic anisotropy of several hundred wavenumbers can be engineered. By using high pressure, we show how the magnetic anisotropy is strongly influenced by small structural distortions. Using a combination of high pressure X-ray diffraction, ab initio methods and high pressure magnetic measurements, we find that hydrostatic pressure lowers both the trigonal symmetry and axial anisotropy, while increasing the rhombic anisotropy. The ligand–metal–ligand angles in the equatorial plane are found to play a crucial role in tuning the energy separation between the dx2−y2 and dxy orbitals, which is the determining factor that controls the magnitude of the axial anisotropy. These results demonstrate that the combination of high pressure techniques with ab initio studies is a powerful tool that gives a unique insight into the design of systems that show giant magnetic anisotropy.

KW - magnetic anisotropy

KW - trigonal bipyramidal Ni(II)

KW - high pressure

KW - X-ray diffraction

U2 - 10.1039/C7SC04460G

DO - 10.1039/C7SC04460G

M3 - Article

VL - 9

SP - 1551

EP - 1559

JO - Chemical Science

T2 - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 6

ER -