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Polyfunctional Lewis Acids: Intriguing Solid‐State Structure and Selective Detection and Discrimination of Nitroaromatic Explosives
Author(s) -
Swamy P Chinna Ayya,
Thilagar Pakkirisamy
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500727
Subject(s) - picric acid , lewis acids and bases , chemistry , supramolecular chemistry , quenching (fluorescence) , explosive material , porphyrin , solid state , intermolecular force , photochemistry , combinatorial chemistry , fluorescence , organic chemistry , crystal structure , molecule , physics , quantum mechanics , catalysis
Synthesis and crystal structures of three porphyrin‐based polyfunctional Lewis acids 1 – 3 are reported. Intermolecular HgCl ⋅⋅⋅ HgCl (linear and μ‐type) interactions in the solid state of the peripherally ArHgCl‐decorated compound 3 lead to a fascinating 3D supramolecular architecture. Compound 3 shows a selective fluorescence quenching response to picric acid and discriminates other nitroaromatic‐based explosives. For the first time, an electron‐deficient polyfunctional Lewis acid is shown to be useful for the selective detection and discrimination of nitroaromatic explosives. The Stern–Volmer quenching constant and detection limits of compound 3 for picric acid are the best among the reported small‐molecular receptors for nitroaromatic explosives. The electronic structure, Lewis acidity, and selective sensing characteristics of 3 are well corroborated by DFT calculations.