EPR spectroscopy of [Fe2O2(5-Et3-TPA) 2]3+

Electronic origin of the unique spin-Hamiltonian parameters of the Fe2III,IVO2 diamond core

Andrew J. Skulan, Melissa A. Hanson, Hua-Fen Hsu, Yanhong Dong, Lawrence Que, Edward I. Solomon

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

The electronic origins of the magnetic signatures of [Fe2O 2(5-Et3-TPA)2](ClO4)3, where 5-Et3-TPA = tris(5-ethyl-2-pyridylmethyl)amine, were investigated by density functional calculations. These signatures consist of a near-axial EPR spectrum, anisotropic superhyperfine broadening upon 17O substitution in the Fe2O2 core, and an unusually large, positive zero-field splitting parameter, D = 38 ± 3 cm-1. Density functional calculations identify the anisotropic 17O superhyperfine broadening to be due to a preponderance of oxo 2p density perpendicular to the plane of the Fe2O2 core in the three singly occupied molecular orbitals of the S = 3/2 ground state. The near-axial g-matrix arises from ΔS = 0 spin-orbit mixing between the singly and doubly occupied dπ orbitals of the iron d-manifold. The large D is due to ΔS = ± 1 spin-orbit mixing with low-lying dπ excited states. These experimental observables reflect the dominance of iron-oxo (rather than Fe-Fe) bonding in the Fe2O 2 core, and define the low-lying valence orbitals responsible for reactivity.

Original languageEnglish
Pages (from-to)6489-6496
Number of pages8
JournalInorganic Chemistry
Volume42
Issue number20
DOIs
Publication statusPublished - 2003 Oct 6

Fingerprint

Hamiltonians
Diamond
Density functional theory
Paramagnetic resonance
Orbits
Iron
diamonds
Spectroscopy
Molecular orbitals
electronics
Excited states
Ground state
spectroscopy
Amines
orbits
iron
orbitals
Substitution reactions
magnetic signatures
molecular orbitals

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Skulan, Andrew J. ; Hanson, Melissa A. ; Hsu, Hua-Fen ; Dong, Yanhong ; Que, Lawrence ; Solomon, Edward I. / EPR spectroscopy of [Fe2O2(5-Et3-TPA) 2]3+ : Electronic origin of the unique spin-Hamiltonian parameters of the Fe2III,IVO2 diamond core. In: Inorganic Chemistry. 2003 ; Vol. 42, No. 20. pp. 6489-6496.
@article{b31a7fd1c65746e9b31620efeea34f99,
title = "EPR spectroscopy of [Fe2O2(5-Et3-TPA) 2]3+: Electronic origin of the unique spin-Hamiltonian parameters of the Fe2III,IVO2 diamond core",
abstract = "The electronic origins of the magnetic signatures of [Fe2O 2(5-Et3-TPA)2](ClO4)3, where 5-Et3-TPA = tris(5-ethyl-2-pyridylmethyl)amine, were investigated by density functional calculations. These signatures consist of a near-axial EPR spectrum, anisotropic superhyperfine broadening upon 17O substitution in the Fe2O2 core, and an unusually large, positive zero-field splitting parameter, D = 38 ± 3 cm-1. Density functional calculations identify the anisotropic 17O superhyperfine broadening to be due to a preponderance of oxo 2p density perpendicular to the plane of the Fe2O2 core in the three singly occupied molecular orbitals of the S = 3/2 ground state. The near-axial g-matrix arises from ΔS = 0 spin-orbit mixing between the singly and doubly occupied dπ orbitals of the iron d-manifold. The large D is due to ΔS = ± 1 spin-orbit mixing with low-lying dπ excited states. These experimental observables reflect the dominance of iron-oxo (rather than Fe-Fe) bonding in the Fe2O 2 core, and define the low-lying valence orbitals responsible for reactivity.",
author = "Skulan, {Andrew J.} and Hanson, {Melissa A.} and Hua-Fen Hsu and Yanhong Dong and Lawrence Que and Solomon, {Edward I.}",
year = "2003",
month = "10",
day = "6",
doi = "10.1021/ic034170z",
language = "English",
volume = "42",
pages = "6489--6496",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "20",

}

EPR spectroscopy of [Fe2O2(5-Et3-TPA) 2]3+ : Electronic origin of the unique spin-Hamiltonian parameters of the Fe2III,IVO2 diamond core. / Skulan, Andrew J.; Hanson, Melissa A.; Hsu, Hua-Fen; Dong, Yanhong; Que, Lawrence; Solomon, Edward I.

In: Inorganic Chemistry, Vol. 42, No. 20, 06.10.2003, p. 6489-6496.

Research output: Contribution to journalArticle

TY - JOUR

T1 - EPR spectroscopy of [Fe2O2(5-Et3-TPA) 2]3+

T2 - Electronic origin of the unique spin-Hamiltonian parameters of the Fe2III,IVO2 diamond core

AU - Skulan, Andrew J.

AU - Hanson, Melissa A.

AU - Hsu, Hua-Fen

AU - Dong, Yanhong

AU - Que, Lawrence

AU - Solomon, Edward I.

PY - 2003/10/6

Y1 - 2003/10/6

N2 - The electronic origins of the magnetic signatures of [Fe2O 2(5-Et3-TPA)2](ClO4)3, where 5-Et3-TPA = tris(5-ethyl-2-pyridylmethyl)amine, were investigated by density functional calculations. These signatures consist of a near-axial EPR spectrum, anisotropic superhyperfine broadening upon 17O substitution in the Fe2O2 core, and an unusually large, positive zero-field splitting parameter, D = 38 ± 3 cm-1. Density functional calculations identify the anisotropic 17O superhyperfine broadening to be due to a preponderance of oxo 2p density perpendicular to the plane of the Fe2O2 core in the three singly occupied molecular orbitals of the S = 3/2 ground state. The near-axial g-matrix arises from ΔS = 0 spin-orbit mixing between the singly and doubly occupied dπ orbitals of the iron d-manifold. The large D is due to ΔS = ± 1 spin-orbit mixing with low-lying dπ excited states. These experimental observables reflect the dominance of iron-oxo (rather than Fe-Fe) bonding in the Fe2O 2 core, and define the low-lying valence orbitals responsible for reactivity.

AB - The electronic origins of the magnetic signatures of [Fe2O 2(5-Et3-TPA)2](ClO4)3, where 5-Et3-TPA = tris(5-ethyl-2-pyridylmethyl)amine, were investigated by density functional calculations. These signatures consist of a near-axial EPR spectrum, anisotropic superhyperfine broadening upon 17O substitution in the Fe2O2 core, and an unusually large, positive zero-field splitting parameter, D = 38 ± 3 cm-1. Density functional calculations identify the anisotropic 17O superhyperfine broadening to be due to a preponderance of oxo 2p density perpendicular to the plane of the Fe2O2 core in the three singly occupied molecular orbitals of the S = 3/2 ground state. The near-axial g-matrix arises from ΔS = 0 spin-orbit mixing between the singly and doubly occupied dπ orbitals of the iron d-manifold. The large D is due to ΔS = ± 1 spin-orbit mixing with low-lying dπ excited states. These experimental observables reflect the dominance of iron-oxo (rather than Fe-Fe) bonding in the Fe2O 2 core, and define the low-lying valence orbitals responsible for reactivity.

UR - http://www.scopus.com/inward/record.url?scp=0141646599&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0141646599&partnerID=8YFLogxK

U2 - 10.1021/ic034170z

DO - 10.1021/ic034170z

M3 - Article

VL - 42

SP - 6489

EP - 6496

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 20

ER -