Heteroleptic Pt(II)-dithiolene-based Colorimetric Chemosensors: Selectivity Control for Hg(II) Ion Sensing

Hg²⁺ ions can accumulate in the natural environment and in organisms, where they cause damage to the central nervous system. Therefore, the detection of Hg²⁺ ions is essential for monitoring environmental contamination and human health. Herein, we demonstrate a simple method for tuning chemosensor signal ratios that significantly increased chemosensor selectivity for Hg²⁺ detection. Selectivity tuning was accomplished for chemosensors of the type (diphosphine)Pt(dmit), bearing the two different terminal groups 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis[bis(pentafluorophenyl)phosphino]ethane) (dfppe) due to the modulation of specific intermolecular interactions between the dmit ligand and Hg²⁺ ion. The structure exhibited a large pseudo-Stokes shift, which was advantageous for the internal reference signal and for eliminating potential artifacts. Straightforward chain-end manipulation enabled the tuning of chemosensor properties without additional chemical alterations. Based on these findings, we propose a new platform for improving the selectivity and sensitivity of colorimetric cation sensors. The results of this study will facilitate the designing of organic materials whose certain properties can be enhanced through precise control of the materials' chemical hybridization by simple functional end-group manipulation.