Abstract
The terminal >CS group in 1,3-dithiole-2-thione-4,5dithiolate (dmit) ligand of (dppe)Pt(dmit) (dppe: 1,2-bis(diphenylphosphino)ethane) is known to be coordinated to Hg2+ ion. This is clearly shown by the bathochromic shift of the π→π⁎ transition band in H2O/CH3CN solution (1:1 v/v). The band shifts are strongly anion-dependent. An equimolar amount of HgX2 (Group I: X=ClO4−, TfO−, CH3SO3−, ½SO42−, AcO−, and F−) led to the bathochromic shift, because of strong >CS⋯Hg2+ interaction. In contrast, a mixed band (Group II: X=Br−, Cl−, and SCN−) or no band shift (Group III: Hg(CN)2 and Hg2Cl2) was observed, because of the strong interaction between Hg2+ and the anions. These results are related to the binding constant (K) of Hg2+ ion with (dppe)Pt(dmit) chemosensor. The binding constants of Hg(ClO4)2 (K=2.3×106) and Hg(OTf)2 (K=2.0×106) are larger than those of Group II and III, resulting in complete bathochromic shift of the π→π⁎ transition at [Hg2+]/[(dppe)Pt(dmit)]=0.4.
Published Version
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