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- W2021719096 abstract "Abstract The EPR of exchange-coupled Fe(C 2 O 4 ) 2 2− and C 2 O 4 − is observed after the photolysis and heating of Fe(C 2 O 4 ) 3 3− in NaMgAl(C 2 O 4 ) 3 ·9H 2 O or K 3 Al(C 2 O 4 ) 3 ·3H 2 O single-crystal hosts. The small 0.052 cm −1 antiferromagnetic coupling is determined from the g anisotropy (the x, y, z principal values are 2.0891, 2.0346 and 1.9970 respectively) and the temperature dependence of the EPR of the lowest Framers doublet of the coupled spin system. The Fe(C 2 O 4 ) 2 2− spin Hamiltonian parameters ( D = 17 cm −1 , E = 3.3 cm −1 , g xx = 2.35, g yy = 2.47 and g zz = 2.077) and the axial and rhombic distortion parameters D = −173 cm −1 , E = −27 cm −1 , respectively, were also determined from the data. The axial direction of the distorted square-planar arrangement of the inner oxygens of Fe(C 2 O 4 ) 2 2− lies only 14.2° from the two-fold axis of the Fe(C 2 O 4 ) 3 3− precursor and the axis of the rhombic distortion (the x axis) lies 54.8° from the three-fold axis of the precursor. It is suggested that the population distributions, the anisotropies and the differences in the spin-lattice relaxation rates between the Fe(C 2 O 4 ) 2 2− spin levels lead to the observation of EPR in only one of the Kramers doublets. The well-oriented nature of the product weighs against the dissociation of C 2 O 4 − into CO 2 − and CO 2 in the crystal. The absence of proton hyperfine structure in the spectrum shows that the protonation of C 2 O 4 − (from the crystal waters of hydration) does not occur, as it evidently does in solution. Comparison of results in the two crystal hosts shows that the ratio of thermal recombination of the photolysis product (which has no EPR spectrum) to Fe(C 2 O 4 ) 3 3− and dissociation to Fe(C 2 O 4 ) 2 2− and C 2 O 4 − varies from ligand to ligand and from host to host. The ratio appears to be very sensitive to the orientation of the reacting ligand and to the crystal packing around it." @default.
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- W2021719096 date "1989-02-01" @default.
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- W2021719096 title "A study of ferric trisoxalate photochemistry in single crystals by electron paramagnetic resonance. An intermediate exchange-coupled ferrous bisoxalate-radical species" @default.
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- W2021719096 doi "https://doi.org/10.1016/0301-0104(89)85001-3" @default.
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