Short communicationAnion-dependent Hg2 +-sensing of colorimetric (dppe)Pt(dmit) chemosensor (dppe: 1,2-bis(diphenylphosphino)ethane; dmit: 1,3-dithiole-2-thione-4,5-dithiolate)

Add time:09/27/2019    Source:sciencedirect.com

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.

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