Solvatochromism of [diamine-N,N'-polycarboxylato]chromium(III) and -cobalt(III) complexes.
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Visible absorption spectra of [diamine-<I>N</I>,<I>N</I>′-polycarboxylato]chromium(III) and -cobalt(III) complexes were measured in twelve different solvents. The diamine-<I>N</I>,<I>N</I>′-polycarboxylates used in this work were ethylenediamine-<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetraacetate (edta<SUP>4−</SUP>), 1,2-cyclohexanediamine-<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetraacetate (cydta<SUP>4−</SUP>), <I>N</I>′-(2-hydroxyethyl)ethylenediamine-<I>N</I>,<I>N</I>,<I>N</I>′-triacetate(hedtra<SUP>3−</SUP>), and <I>N</I>′-methylethylenediamine-<I>N</I>,<I>N</I>,<I>N</I>′-triacetate (medtra<SUP>3−</SUP>). The first d–d absorption maxima of these complexes depend considerably on the solvents. From the solvatochromic behaviors of these complexes, it was concluded that solid complexes, K[Co(edta)]·2H<SUB>2</SUB>O, K[Co(cydta)]·3H<SUB>2</SUB>O, [Co(hedtra)(H<SUB>2</SUB>O)], [Co(medtra)(H<SUB>2</SUB>O)]·3H<SUB>2</SUB>O, Na[Cr(cydta)]·4.5H<SUB>2</SUB>O, and probably K[Cr(edta)]·2H<SUB>2</SUB>O, dissolve in the solvents while holding their first coordination sphere intact; in some solvents, however, [Cr(medtra)(H<SUB>2</SUB>O)]·1.5H<SUB>2</SUB>O and [Cr(hedtra)(H<SUB>2</SUB>O)]·1.5H<SUB>2</SUB>O undergo substitutions of the coordinated water molecule to form [Cr(medtra)(solvent)] and [Cr(hedtra)(solvent)], respectively.
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