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For the concentrated solution (1.5 mM) the spectra showed an additional broad absorption-derivative signal at g ≈ 2 that changed upon dilution. However, the pattern persisted even at 20 μM concentration and varied for different preparations. We suppose that the neutral complexes tend to aggregate in solution. The resulting enhanced intermolecular spin-spin interaction could give rise to the collapsed signal at g ≈ 2. On the other hand, such a feature could not be reasonably well simulated with the usual rhombic spin Hamiltonian [Eq. (4)].
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x′x′ oriented in the z direction.
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0345275618
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The large asymmetry parameter was essentially confirmed by the symmetric hyperfine pattern of a magnetically perturbed measurement (7 T) at 160 K, which indicated that η is close to 1. However, under these conditions spin relaxation appeared to be in an intermediate range with respect to the nuclear precession rate as the spectrum was not satisfactorily resolved. We therefore refrain from depicting the result of a preliminary simulation, performed with the Hamiltonian [Eqs. (4),(5)] in the limit of fast or slow relaxation.
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A similar effect is discussed for 3s electrons that can be polarized by negative spin density in the overlap region of metal - ligand bonds, see ref. [31].
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