Anion-binding-induced selective aggregation and self-degradation: Influence of positional isomerism on the anion selectivity and mode of binding of an imine-based receptor.

Imine based positional isomers (8E)-N-(4-((E)-(perfluorophenylimino)methyl)benzylidene)-2,3,4,5,6-pentafluorobenzenamine, L and (10E)-N-(3-(E-Perfluorophenylimino)methyl)benzylidene)-2,3,4,5,6-pentafluorobenzenamine, L1 have been designed, and synthesized by functionalizing two electron deficient aromatic moieties at the para-para'/ortho-ortho' positions in the phenyl core of the L and L1 respectively. The responses of L and L1 towards various anionic species are examined. The positional isomers L and L1 differs not only by showing distinguishable color change upon addition of anions but also differentiates themselves by the way of self-assembling together upon binding with cyanide anion. The naked-eye colorimetric experiments, UV-Vis, Nuclear Magnetic Resonance, and Infra-Red spectroscopic analyses reveal that the isomer L binds fluoride anion through 2:1 stoichiometry ratio. Unlike fluoride complex, the isomer L form aggregates while binding with cyanide ion. On the other hand, isomer L1 does not show any instant color change upon additions of any anion. Interestingly, after thirty minutes, only the color of the cyanide complex is turned into dark brown. While analyzing the spectroscopic results of cyanide complex of L1, it is found that the cyanide complex begins to decompose and finally it is completely decomposed within 30 min. This unprecedented phenomenon about the colorimetric sensing of cyanide and destruction of cyanide complex with respect to time has not been reported in the literature yet. To the best of our knowledge this is the first example of study of sensing controlling the selectivity, mode of binding, self-aggregating and degradation properties of anionic complexes under the influence of positional isomeric effects. This present investigation provides simple and effective strategy to construct the sensor molecules with tunable binding properties in terms of easy to prepare as well as easy to use as a colorimetric sensor. _____________________________________________________________________________________________________.