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In all cases, the g-values were in the range 2.01-2.08, and variations in these values had only negligible effects on the quality of the resulting fits. Specifically, our analysis revealed that the overall shapes of the VTVH-MCD magnetization curves are determined principally by the ZFS parameters, not the g-values.
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13644253336
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note
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4cyclam over the pyridyl-pendant diazacyclooctane ligand.
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51
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13644266414
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note
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The geometric parameter τ is defined as τ = |(β - α)|/60, where α and β are the two trans basal angles in psuedo-square pyramidal geometry (see ref 41). In idealized square-planar geometries, α = β, but trigonal distortions result in α ≠ β.
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note
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58
-
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13644251070
-
-
note
-
Although the solid-state sample of 2 contains two crystallographically distinct complexes (cations I and II), the structural differences are too small to cause the appearance of two sets of bands that can be resolved in the MCD spectrum but may possibly lead to a general broadening of the bands.
-
-
-
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59
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1242319484
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60
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13644270867
-
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note
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-1. However, in all instances, the ZFS parameters that provided the best fits of the low-energy VTVH-MCD data sets also provided excellent fits of the corresponding high-energy data sets.
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-
-
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61
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0034638855
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63
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13644250228
-
-
note
-
For these S = 2 complexes, spin polarization lowers the energies of the majority-spin (i.e., spin-up) Fe d orbitals relative to their minority-spin (i.e., spin-down) counterparts, resulting in substantial mixing of the former with ligand-based orbitals. The natures of the Fe-ligand bonding interactions are therefore inferred from the ligand- and Fe d-based spin-down MOs that are considerably less mixed than their spin-up counterparts.
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-
-
-
64
-
-
13644261710
-
-
note
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2-based orbitals.
-
-
-
-
65
-
-
13644270866
-
-
note
-
x2-y2 orbitals.
-
-
-
-
66
-
-
13644269913
-
-
note
-
2 π*-acceptor orbitals.
-
-
-
-
67
-
-
13644258006
-
-
note
-
For complex 2, the angles reported in the text are averaged over both crystallographically independent cations.
-
-
-
-
68
-
-
13644255574
-
-
note
-
Note that for both complexes deviations of these angles from 90° give rise to somewhat mixed σ- and π-bonding interactions.
-
-
-
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69
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1542378734
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Solomon, E. I.; Szilagyi, R. K.; George, S. D.; Basumallick, L. Chem. Rev. 2004, 104, 419-458.
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70
-
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13644258615
-
-
note
-
-1 to facilitate comparison with the experimental spectrum.
-
-
-
-
71
-
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13644266415
-
-
note
-
It is important to note that bands that are intense in the absorption spectrum are often weak in the MCD spectrum, and it is therefore not surprising that the relative intensities of bands 6 and 7 are dramatically different in the two spectra.
-
-
-
-
72
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13644268876
-
-
note
-
-1 (Figure 4).
-
-
-
-
73
-
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13644267238
-
-
note
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-1. It is therefore apparent that, although DFT provides a qualitatively correct Fe d-orbital splitting pattern for 3, the experimental Fe d-orbital splitting pattern is, in fact, reminiscent of an "effective" electronic symmetry intermediate between trigonal bipyramidal and square pyramidal.
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75
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0029274711
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76
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13644249404
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note
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red (see ref 4).
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77
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1542317537
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