182
M. Gruden et al.
53. Duboc C, Gennari M (2015) Experimental techniques for determining spin states. In: Spin
states in biochemistry and inorganic chemistry. Wiley, pp 59–83. https://doi.org/10.1002/
9781118898277.ch4
54. Neese F (2006) Importance of direct spin-spin coupling and spin-flip excitations for the zerofield splitting of transition metal complexes: a case study. J Am Chem Soc 128:10213–10222.
https://doi.org/10.1021/ja061798a
55. Sousa C, de Graaf C (2015) Ab initio wavefunction approaches to spin states. In: Spin
states in biochemistry and inorganic chemistry. Wiley, pp 35–57. https://doi.org/10.1002/
9781118898277.ch3
56. Daul CA, Zlatar M, Gruden-Pavlovic M, Swart M (2015) Application of density functional
and density functional based ligand field theory to spin states. In: Spin states in biochemistry
and inorganic chemistry. Wiley, pp 7–34. https://doi.org/10.1002/9781118898277.ch2
57. Pederson MR, Khanna SN (1999) Magnetic anisotropy barrier for spin tunneling in Mn 12 O 12
molecules. Phys Rev B 60:9566–9572
58. Neese F, Solomon EI (1998) Calculation of zero-field splittings, g-values, and the relativistic
nephelauxetic effect in transition metal complexes. Application to high-spin ferric complexes.
Inorg Chem 37:6568–6582
59. Atanasov M, Daul CA, Rauzy C (2003) New insights into the effects of covalency on the ligand
field parameters: a DFT study. Chem Phys Lett 367:737–746. https://doi.org/10.1016/s00092614(02)01762-1
60. Sessoli R, Gatteschi D, Caneschi A, Novak MA (1993) Magnetic bistability in a metal-ion
cluster. Nature 365:141–143
61. Duboc C, Ganyushin D, Sivalingam K, Collomb M-N, Neese F (2010) Systematic theoretical
study of the zero-field splitting in coordination complexes of Mn(III). Density functional theory
versus multireference wave function approaches. J Phys Chem A 114:10750–10758. https://
doi.org/10.1021/jp107823s
62. Duboc C (2016) Determination and prediction of the magnetic anisotropy of Mn ions. Chem
Soc Rev 45:5834–5847. https://doi.org/10.1039/C5CS00898K
63. Zlatar M et al (2016) Origin of the zero-field splitting in mononuclear octahedral Mn IV complexes: a combined experimental and theoretical investigation. Inorg Chem 55:1192–1201.
https://doi.org/10.1021/acs.inorgchem.5b02368
64. Leto DF, Massie AA, Colmer HE, Jackson TA (2016) X-Band electron paramagnetic resonance
comparison of mononuclear Mn IV -oxo and Mn IV -hydroxo complexes and quantum chemical
investigation of Mn IV zero-field splitting. Inorg Chem 55:3272–3282. https://doi.org/10.1021/
acs.inorgchem.5b02309
65. Barra AL, Gatteschi D, Sessoli R, Abbati GL, Cornia A, Fabretti AC, Uytterhoeven MG (1997)
Electronic structure of manganese(III) compounds from high-frequency EPR spectra. Angew
Chem Int Ed 36:2329–2331
66. Goldberg DP, Telser J, Krzystek J, Montalban AG, Brunel L-C, Barrett AGM, Hoffman BM
(1997) EPR spectra from “EPR-silent” species: high-field EPR spectroscopy of manganese(III)
porphyrins. J Am Chem Soc 119:8722–8723. https://doi.org/10.1021/ja971169o
67. Duboc C, Collomb MN (2009) Multifrequency high-field EPR investigation of a mononuclear
manganese(IV) complex. Chem Commun 2715–2717. https://doi.org/10.1039/b901185d
68. Brazzolotto D et al (2016) An experimental and theoretical investigation on pentacoordinated
cobalt(III) complexes with an intermediate S 1 spin state: how halide ligands affect their
magnetic anisotropy. Chem Eur J 22:925–933. https://doi.org/10.1002/chem.201502997
69. Wang LK et al (2018) Experimental and theoretical identification of the origin of magnetic
anisotropy in intermediate spin iron(III) complexes. Chem Eur J 24:5091–5094. https://doi.
org/10.1002/chem.201705989
70. Duboc C, Phoeung T, Zein S, Pécaut J, Collomb MN, Neese F (2007) Origin of the zero-field
splitting in mononuclear octahedral dihalide Mn-II complexes: an investigation by multifrequency high-field electron paramagnetic resonance and density functional theory. Inorg Chem
46:4905–4916. https://doi.org/10.1021/ic062384l
M. Gruden et al.
53. Duboc C, Gennari M (2015) Experimental techniques for determining spin states. In: Spin
states in biochemistry and inorganic chemistry. Wiley, pp 59–83. https://doi.org/10.1002/
9781118898277.ch4
54. Neese F (2006) Importance of direct spin-spin coupling and spin-flip excitations for the zerofield splitting of transition metal complexes: a case study. J Am Chem Soc 128:10213–10222.
https://doi.org/10.1021/ja061798a
55. Sousa C, de Graaf C (2015) Ab initio wavefunction approaches to spin states. In: Spin
states in biochemistry and inorganic chemistry. Wiley, pp 35–57. https://doi.org/10.1002/
9781118898277.ch3
56. Daul CA, Zlatar M, Gruden-Pavlovic M, Swart M (2015) Application of density functional
and density functional based ligand field theory to spin states. In: Spin states in biochemistry
and inorganic chemistry. Wiley, pp 7–34. https://doi.org/10.1002/9781118898277.ch2
57. Pederson MR, Khanna SN (1999) Magnetic anisotropy barrier for spin tunneling in Mn 12 O 12
molecules. Phys Rev B 60:9566–9572
58. Neese F, Solomon EI (1998) Calculation of zero-field splittings, g-values, and the relativistic
nephelauxetic effect in transition metal complexes. Application to high-spin ferric complexes.
Inorg Chem 37:6568–6582
59. Atanasov M, Daul CA, Rauzy C (2003) New insights into the effects of covalency on the ligand
field parameters: a DFT study. Chem Phys Lett 367:737–746. https://doi.org/10.1016/s00092614(02)01762-1
60. Sessoli R, Gatteschi D, Caneschi A, Novak MA (1993) Magnetic bistability in a metal-ion
cluster. Nature 365:141–143
61. Duboc C, Ganyushin D, Sivalingam K, Collomb M-N, Neese F (2010) Systematic theoretical
study of the zero-field splitting in coordination complexes of Mn(III). Density functional theory
versus multireference wave function approaches. J Phys Chem A 114:10750–10758. https://
doi.org/10.1021/jp107823s
62. Duboc C (2016) Determination and prediction of the magnetic anisotropy of Mn ions. Chem
Soc Rev 45:5834–5847. https://doi.org/10.1039/C5CS00898K
63. Zlatar M et al (2016) Origin of the zero-field splitting in mononuclear octahedral Mn IV complexes: a combined experimental and theoretical investigation. Inorg Chem 55:1192–1201.
https://doi.org/10.1021/acs.inorgchem.5b02368
64. Leto DF, Massie AA, Colmer HE, Jackson TA (2016) X-Band electron paramagnetic resonance
comparison of mononuclear Mn IV -oxo and Mn IV -hydroxo complexes and quantum chemical
investigation of Mn IV zero-field splitting. Inorg Chem 55:3272–3282. https://doi.org/10.1021/
acs.inorgchem.5b02309
65. Barra AL, Gatteschi D, Sessoli R, Abbati GL, Cornia A, Fabretti AC, Uytterhoeven MG (1997)
Electronic structure of manganese(III) compounds from high-frequency EPR spectra. Angew
Chem Int Ed 36:2329–2331
66. Goldberg DP, Telser J, Krzystek J, Montalban AG, Brunel L-C, Barrett AGM, Hoffman BM
(1997) EPR spectra from “EPR-silent” species: high-field EPR spectroscopy of manganese(III)
porphyrins. J Am Chem Soc 119:8722–8723. https://doi.org/10.1021/ja971169o
67. Duboc C, Collomb MN (2009) Multifrequency high-field EPR investigation of a mononuclear
manganese(IV) complex. Chem Commun 2715–2717. https://doi.org/10.1039/b901185d
68. Brazzolotto D et al (2016) An experimental and theoretical investigation on pentacoordinated
cobalt(III) complexes with an intermediate S 1 spin state: how halide ligands affect their
magnetic anisotropy. Chem Eur J 22:925–933. https://doi.org/10.1002/chem.201502997
69. Wang LK et al (2018) Experimental and theoretical identification of the origin of magnetic
anisotropy in intermediate spin iron(III) complexes. Chem Eur J 24:5091–5094. https://doi.
org/10.1002/chem.201705989
70. Duboc C, Phoeung T, Zein S, Pécaut J, Collomb MN, Neese F (2007) Origin of the zero-field
splitting in mononuclear octahedral dihalide Mn-II complexes: an investigation by multifrequency high-field electron paramagnetic resonance and density functional theory. Inorg Chem
46:4905–4916. https://doi.org/10.1021/ic062384l