High-frequency EPR study of a new mononuclear manganese(III) complex

[(Terpy)Mn(N3)3] (terpy = 2,2′:6′,2′-terpyridine)

J. Limburg, J. S. Vrettos, R. H. Crabtree, Gary W Brudvig, J. C. De Paula, A. Hassan, A. L. Barra, C. Duboc-Toia, M. N. Collomb

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Abstract

The isolation and structural characterization of [(terpy)MnIII(N3)3], complex 1, is reported (terpy = 2,2′:6′,2-″terpyridine). Complex 1, a product of the reaction between the mixed-valence dimer[(terpy)(H2O)MnIII(O) 2-MnIV(OH2)(terpy)] (NO3)3 and NaN3, crystallizes in a triclinic system, space group P1, a = 8.480(1) Å b = 8.9007(2) Å, c = 12.109(2) Å, α = 93.79(1)°, β = 103.17(1)°, γ = 103.11(1)° and Z = 2. Complex 1 exhibits a Jahn-Teller distortion of the octahedron characteristic of a six-coordinated high-spin Mn(III). A vibrational spectroscopic study was performed. The vasym(N3) mode of complex 1 appears in the IR as a strong band at 2035 cm-1 with a less intense feature at 2072 cm-1, and in the FT-Raman as a strong band at 2071 cm-1 with a weaker broad band at 2046 cm-1. The electronic properties of complex 1 were investigated using a high-field and high-frequency EPR study (190-475 GHz). The different spin Hamiltonian parameters have been determined (D = -3.29 (±0.01) cm-1, E = 0.48 (±0.01) cm-1, E′= 0.53 (±0.01) cm-1, gx = 2.00 (±0.005), gy = 1.98 (±0.005), gz = 2.01 (±0.005)). These parameters are in agreement with the geometry of complex 1 observed in the crystal structure, a D <0 related to the elongated distortion, and a value of E/D close to 0.2 as expected from the highly distorted octahedron. The two values of the E-parameter are explained by the presence of two slightly different structural forms of complex 1 in the crystal lattice. A second hypothesis was explored to explain the experimental data. The calculation for the simulation was done taking into account that the g and D tensors are not collinear due to the low symmetry of complex 1. In that case, the spin Hamiltonian parameters found are D = -3.29 (±0.01) cm-1, E = 0.51 (±0.01) cm-1, gx = 2.00 (±0.005), gy = L98 (±0.005), and g, = 2.01 (±0.005).

Original languageEnglish
Pages (from-to)1698-1703
Number of pages6
JournalInorganic Chemistry
Volume40
Issue number7
DOIs
Publication statusPublished - Mar 26 2001

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Hamiltonians
Manganese
Paramagnetic resonance
manganese
Jahn-Teller effect
Sodium Azide
Crystal lattices
Electronic properties
Dimers
Tensors
Crystal structure
Geometry
crystal lattices
isolation
dimers
tensors
broadband
valence
crystal structure
(terpy)Mn(N3)3

ASJC Scopus subject areas

  • Inorganic Chemistry

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High-frequency EPR study of a new mononuclear manganese(III) complex : [(Terpy)Mn(N3)3] (terpy = 2,2′:6′,2′-terpyridine). / Limburg, J.; Vrettos, J. S.; Crabtree, R. H.; Brudvig, Gary W; De Paula, J. C.; Hassan, A.; Barra, A. L.; Duboc-Toia, C.; Collomb, M. N.

In: Inorganic Chemistry, Vol. 40, No. 7, 26.03.2001, p. 1698-1703.

Research output: Contribution to journalArticle

Limburg, J, Vrettos, JS, Crabtree, RH, Brudvig, GW, De Paula, JC, Hassan, A, Barra, AL, Duboc-Toia, C & Collomb, MN 2001, 'High-frequency EPR study of a new mononuclear manganese(III) complex: [(Terpy)Mn(N3)3] (terpy = 2,2′:6′,2′-terpyridine)', Inorganic Chemistry, vol. 40, no. 7, pp. 1698-1703. https://doi.org/10.1021/ic001118j
Limburg, J. ; Vrettos, J. S. ; Crabtree, R. H. ; Brudvig, Gary W ; De Paula, J. C. ; Hassan, A. ; Barra, A. L. ; Duboc-Toia, C. ; Collomb, M. N. / High-frequency EPR study of a new mononuclear manganese(III) complex : [(Terpy)Mn(N3)3] (terpy = 2,2′:6′,2′-terpyridine). In: Inorganic Chemistry. 2001 ; Vol. 40, No. 7. pp. 1698-1703.
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title = "High-frequency EPR study of a new mononuclear manganese(III) complex: [(Terpy)Mn(N3)3] (terpy = 2,2′:6′,2′-terpyridine)",
abstract = "The isolation and structural characterization of [(terpy)MnIII(N3)3], complex 1, is reported (terpy = 2,2′:6′,2-″terpyridine). Complex 1, a product of the reaction between the mixed-valence dimer[(terpy)(H2O)MnIII(O) 2-MnIV(OH2)(terpy)] (NO3)3 and NaN3, crystallizes in a triclinic system, space group P1, a = 8.480(1) {\AA} b = 8.9007(2) {\AA}, c = 12.109(2) {\AA}, α = 93.79(1)°, β = 103.17(1)°, γ = 103.11(1)° and Z = 2. Complex 1 exhibits a Jahn-Teller distortion of the octahedron characteristic of a six-coordinated high-spin Mn(III). A vibrational spectroscopic study was performed. The vasym(N3) mode of complex 1 appears in the IR as a strong band at 2035 cm-1 with a less intense feature at 2072 cm-1, and in the FT-Raman as a strong band at 2071 cm-1 with a weaker broad band at 2046 cm-1. The electronic properties of complex 1 were investigated using a high-field and high-frequency EPR study (190-475 GHz). The different spin Hamiltonian parameters have been determined (D = -3.29 (±0.01) cm-1, E = 0.48 (±0.01) cm-1, E′= 0.53 (±0.01) cm-1, gx = 2.00 (±0.005), gy = 1.98 (±0.005), gz = 2.01 (±0.005)). These parameters are in agreement with the geometry of complex 1 observed in the crystal structure, a D <0 related to the elongated distortion, and a value of E/D close to 0.2 as expected from the highly distorted octahedron. The two values of the E-parameter are explained by the presence of two slightly different structural forms of complex 1 in the crystal lattice. A second hypothesis was explored to explain the experimental data. The calculation for the simulation was done taking into account that the g and D tensors are not collinear due to the low symmetry of complex 1. In that case, the spin Hamiltonian parameters found are D = -3.29 (±0.01) cm-1, E = 0.51 (±0.01) cm-1, gx = 2.00 (±0.005), gy = L98 (±0.005), and g, = 2.01 (±0.005).",
author = "J. Limburg and Vrettos, {J. S.} and Crabtree, {R. H.} and Brudvig, {Gary W} and {De Paula}, {J. C.} and A. Hassan and Barra, {A. L.} and C. Duboc-Toia and Collomb, {M. N.}",
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TY - JOUR

T1 - High-frequency EPR study of a new mononuclear manganese(III) complex

T2 - [(Terpy)Mn(N3)3] (terpy = 2,2′:6′,2′-terpyridine)

AU - Limburg, J.

AU - Vrettos, J. S.

AU - Crabtree, R. H.

AU - Brudvig, Gary W

AU - De Paula, J. C.

AU - Hassan, A.

AU - Barra, A. L.

AU - Duboc-Toia, C.

AU - Collomb, M. N.

PY - 2001/3/26

Y1 - 2001/3/26

N2 - The isolation and structural characterization of [(terpy)MnIII(N3)3], complex 1, is reported (terpy = 2,2′:6′,2-″terpyridine). Complex 1, a product of the reaction between the mixed-valence dimer[(terpy)(H2O)MnIII(O) 2-MnIV(OH2)(terpy)] (NO3)3 and NaN3, crystallizes in a triclinic system, space group P1, a = 8.480(1) Å b = 8.9007(2) Å, c = 12.109(2) Å, α = 93.79(1)°, β = 103.17(1)°, γ = 103.11(1)° and Z = 2. Complex 1 exhibits a Jahn-Teller distortion of the octahedron characteristic of a six-coordinated high-spin Mn(III). A vibrational spectroscopic study was performed. The vasym(N3) mode of complex 1 appears in the IR as a strong band at 2035 cm-1 with a less intense feature at 2072 cm-1, and in the FT-Raman as a strong band at 2071 cm-1 with a weaker broad band at 2046 cm-1. The electronic properties of complex 1 were investigated using a high-field and high-frequency EPR study (190-475 GHz). The different spin Hamiltonian parameters have been determined (D = -3.29 (±0.01) cm-1, E = 0.48 (±0.01) cm-1, E′= 0.53 (±0.01) cm-1, gx = 2.00 (±0.005), gy = 1.98 (±0.005), gz = 2.01 (±0.005)). These parameters are in agreement with the geometry of complex 1 observed in the crystal structure, a D <0 related to the elongated distortion, and a value of E/D close to 0.2 as expected from the highly distorted octahedron. The two values of the E-parameter are explained by the presence of two slightly different structural forms of complex 1 in the crystal lattice. A second hypothesis was explored to explain the experimental data. The calculation for the simulation was done taking into account that the g and D tensors are not collinear due to the low symmetry of complex 1. In that case, the spin Hamiltonian parameters found are D = -3.29 (±0.01) cm-1, E = 0.51 (±0.01) cm-1, gx = 2.00 (±0.005), gy = L98 (±0.005), and g, = 2.01 (±0.005).

AB - The isolation and structural characterization of [(terpy)MnIII(N3)3], complex 1, is reported (terpy = 2,2′:6′,2-″terpyridine). Complex 1, a product of the reaction between the mixed-valence dimer[(terpy)(H2O)MnIII(O) 2-MnIV(OH2)(terpy)] (NO3)3 and NaN3, crystallizes in a triclinic system, space group P1, a = 8.480(1) Å b = 8.9007(2) Å, c = 12.109(2) Å, α = 93.79(1)°, β = 103.17(1)°, γ = 103.11(1)° and Z = 2. Complex 1 exhibits a Jahn-Teller distortion of the octahedron characteristic of a six-coordinated high-spin Mn(III). A vibrational spectroscopic study was performed. The vasym(N3) mode of complex 1 appears in the IR as a strong band at 2035 cm-1 with a less intense feature at 2072 cm-1, and in the FT-Raman as a strong band at 2071 cm-1 with a weaker broad band at 2046 cm-1. The electronic properties of complex 1 were investigated using a high-field and high-frequency EPR study (190-475 GHz). The different spin Hamiltonian parameters have been determined (D = -3.29 (±0.01) cm-1, E = 0.48 (±0.01) cm-1, E′= 0.53 (±0.01) cm-1, gx = 2.00 (±0.005), gy = 1.98 (±0.005), gz = 2.01 (±0.005)). These parameters are in agreement with the geometry of complex 1 observed in the crystal structure, a D <0 related to the elongated distortion, and a value of E/D close to 0.2 as expected from the highly distorted octahedron. The two values of the E-parameter are explained by the presence of two slightly different structural forms of complex 1 in the crystal lattice. A second hypothesis was explored to explain the experimental data. The calculation for the simulation was done taking into account that the g and D tensors are not collinear due to the low symmetry of complex 1. In that case, the spin Hamiltonian parameters found are D = -3.29 (±0.01) cm-1, E = 0.51 (±0.01) cm-1, gx = 2.00 (±0.005), gy = L98 (±0.005), and g, = 2.01 (±0.005).

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