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Pseudooctahedral Complexes of Vanadium(III): Electronic Structure Investigation by Magnetic and Electronic Spectroscopy.

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Title: Pseudooctahedral Complexes of Vanadium(III): Electronic Structure Investigation by Magnetic and Electronic Spectroscopy.
Authors: Krzystek, J.1, Fiedler, Adam T.2, Sokol, Jennifer J.3, Ozarowski, Andrew1, Zvyagin, S. A.1, Brunold, Thomas C.2, Long, Jeffrey R.3, Brunel, Louis-Claude1, Telser, Joshua4 jtelser@roosevelt.edu
Source: Inorganic Chemistry. 9/6/2004, Vol. 43 Issue 18, p5645-5658. 14p.
Subjects: Spectrum analysis, Magnetic susceptibility, Molecular structure, Particles (Nuclear physics), Tetrahydrofuran
Abstract: A variety of physical methods has been used to probe the non-Kramers, S = 1, V(III) ion in two types of pseudooctahedral complexes: V(acac)3, where acac = anion of 2,4-pentanedione, and VX3(thf)3, where thf = tetrahydrofuran and X = Cl and Br. These methods include tunable frequency and high-field electron paramagnetic resonance (HFEPR) spectroscopy (using frequencies of ∼95–700 GHz and fields up to 25 T) in conjunction with electronic absorption, magnetic circular dichroism (MCD), and variable-temperature variable-field MCD (VTVH- MCD) spectroscopies. Variable-temperature magnetic susceptibility and field-dependent magnetization measurements were also performed. All measurements were conducted on complexes in the solid state (powder or mull samples). The field versus sub-THz wave quantum energy dependence of observed HFEPR resonances yielded the following spin Hamiltonian parameters for V(acac)3: D = +7.470(1) cm-1; E = +1.916(1) cm-1; gx = 1.833(4); gy = 1.72(2); gz = 2.03(2). For VCl3(thf)3, HFEPR detected a single zero-field transition at 15.8 cm-1 (474 GHz), which was insufficient to determine the complete set of spin Hamiltonian parameters. For VBr3(thf)3, however, a particularly rich data set was obtained using tunable-frequency HFEPR, and analysis of this data set gave the folowing: D = -16.162(6) cm-1; E = -3.694(4) cm-1; gx = 1.86(1); gy = 1.90(1); gz = 1.710(4). Analysis of the VTVH-MCD data gave spin Hamiltonian parameters in good agreement with those determined by HFEPR for both V(acac)3 and VBr3(thf)3 and in rough agreement with the estimate for VCl3(thf)3 (D ≈ 10 cm-1, ¦E/D¦ ≈ 0.18), together with the finding that the value of D is negative for both thf complexes. The electronic structures of these V(III) complexes are discussed in terms of their molecular structures and the electronic transitions observed by electronic absorption and MCD spectroscopies. [ABSTRACT FROM AUTHOR]
Copyright of Inorganic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Pseudooctahedral Complexes of Vanadium(III): Electronic Structure Investigation by Magnetic and Electronic Spectroscopy.
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  Data: <searchLink fieldCode="AR" term="%22Krzystek%2C+J%2E%22">Krzystek, J.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Fiedler%2C+Adam+T%2E%22">Fiedler, Adam T.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Sokol%2C+Jennifer+J%2E%22">Sokol, Jennifer J.</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Ozarowski%2C+Andrew%22">Ozarowski, Andrew</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Zvyagin%2C+S%2E+A%2E%22">Zvyagin, S. A.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Brunold%2C+Thomas+C%2E%22">Brunold, Thomas C.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Long%2C+Jeffrey+R%2E%22">Long, Jeffrey R.</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Brunel%2C+Louis-Claude%22">Brunel, Louis-Claude</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Telser%2C+Joshua%22">Telser, Joshua</searchLink><relatesTo>4</relatesTo><i> jtelser@roosevelt.edu</i>
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  Data: <searchLink fieldCode="JN" term="%22Inorganic+Chemistry%22">Inorganic Chemistry</searchLink>. 9/6/2004, Vol. 43 Issue 18, p5645-5658. 14p.
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  Data: <searchLink fieldCode="DE" term="%22Spectrum+analysis%22">Spectrum analysis</searchLink><br /><searchLink fieldCode="DE" term="%22Magnetic+susceptibility%22">Magnetic susceptibility</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink><br /><searchLink fieldCode="DE" term="%22Particles+%28Nuclear+physics%29%22">Particles (Nuclear physics)</searchLink><br /><searchLink fieldCode="DE" term="%22Tetrahydrofuran%22">Tetrahydrofuran</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: A variety of physical methods has been used to probe the non-Kramers, S = 1, V(III) ion in two types of pseudooctahedral complexes: V(acac)3, where acac = anion of 2,4-pentanedione, and VX3(thf)3, where thf = tetrahydrofuran and X = Cl and Br. These methods include tunable frequency and high-field electron paramagnetic resonance (HFEPR) spectroscopy (using frequencies of ∼95–700 GHz and fields up to 25 T) in conjunction with electronic absorption, magnetic circular dichroism (MCD), and variable-temperature variable-field MCD (VTVH- MCD) spectroscopies. Variable-temperature magnetic susceptibility and field-dependent magnetization measurements were also performed. All measurements were conducted on complexes in the solid state (powder or mull samples). The field versus sub-THz wave quantum energy dependence of observed HFEPR resonances yielded the following spin Hamiltonian parameters for V(acac)3: D = +7.470(1) cm-1; E = +1.916(1) cm-1; gx = 1.833(4); gy = 1.72(2); gz = 2.03(2). For VCl3(thf)3, HFEPR detected a single zero-field transition at 15.8 cm-1 (474 GHz), which was insufficient to determine the complete set of spin Hamiltonian parameters. For VBr3(thf)3, however, a particularly rich data set was obtained using tunable-frequency HFEPR, and analysis of this data set gave the folowing: D = -16.162(6) cm-1; E = -3.694(4) cm-1; gx = 1.86(1); gy = 1.90(1); gz = 1.710(4). Analysis of the VTVH-MCD data gave spin Hamiltonian parameters in good agreement with those determined by HFEPR for both V(acac)3 and VBr3(thf)3 and in rough agreement with the estimate for VCl3(thf)3 (D ≈ 10 cm-1, ¦E/D¦ ≈ 0.18), together with the finding that the value of D is negative for both thf complexes. The electronic structures of these V(III) complexes are discussed in terms of their molecular structures and the electronic transitions observed by electronic absorption and MCD spectroscopies. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Data: <i>Copyright of Inorganic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/ic0493503
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      – Code: eng
        Text: English
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        PageCount: 14
        StartPage: 5645
    Subjects:
      – SubjectFull: Spectrum analysis
        Type: general
      – SubjectFull: Magnetic susceptibility
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      – SubjectFull: Molecular structure
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      – SubjectFull: Particles (Nuclear physics)
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      – SubjectFull: Tetrahydrofuran
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      – TitleFull: Pseudooctahedral Complexes of Vanadium(III): Electronic Structure Investigation by Magnetic and Electronic Spectroscopy.
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              Text: 9/6/2004
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