PtII6 nanoscopic cages with an organometallic backbone as sensors for picric acid

Abstract

An organometallic building block 1,3,5-tris(4-trans-Pt(PEt₃)₂I(ethynyl)phenyl)benzene (1) incorporating Pt-ethynyl functionality has been synthesized and characterized. [2 + 3] self-assembly of its nitrate analogue 1,3,5-tris(4-trans-Pt(PEt₃)₂(ONO₂)(ethynyl)phenyl)benzene (2) with “clip” type bidentate donors (L₁–L₃) separately afforded three trigonal prismatic architectures (3a–3c), respectively. All these prisms were characterized and their shapes/sizes are predicted through geometry optimization employing molecular mechanics universal force field (MMUFF) simulation. The extended π-conjugation including the presence of Pt-ethynyl functionality makes them electron rich as well as luminescent in nature. Macrocycles 3b and 3c exhibit fluorescence quenching in solution upon addition of picric acid [PA], which is a common constituent of many explosives. Interestingly, the non-responsive nature of fluorescent intensity towards other electron-deficient nitro-aromatic explosives (NAEs) makes them promising selective sensors for PA with a detection limit predicted to be ppb level. Furthermore, solid-state quenching of fluorescent intensity of the thin film of 3b upon exposure to saturated vapor of picric acid has drawn special attention for infield applications.