Tetramerization of substituted maleonitriles in task specific 2-hydroxylethyl based imidazolium ionic liquids at 120◦C gave corresponding electron rich peripheral substituted thioporphyrazines in moderate yield. The 2-hydroxylethyl imidazolium ionic liquids gave better yields of peripheral substituted thioporphyrazinesin comparison with non-hydroxyl functionalized ionic liquids. Further, these peripherally functionalized porphyrazines containing sulphur are used to investigate spectroscopically the binding studies with palladium(II) and mercury(II) ions. These metal ions are toxic in nature and deserve serious attention in the areaof design of effective separation and efficient micro-sensing techniques. The UV–Vis absorption spectroscopy and fluorescence signalling are mainly used to study peripheral binding of transition metal ions.