Tuned Cd2+ selectivity: Showcase of electronic and regio-effect of π-extended di-2-picolylamine-substituted quinoline-based tolans

Abstract

π -Extended di-2-picolylamine (DPA)-substituted 8-hydroxyquinoline (8-HQ) tolans (2) were synthesized for testing electronic and regio-effects. The electron-poor CN-tolan (2b) showed clear selectivity for Cd2+ (>>Zn2+) over other metal ions via turn-on fluorescence, while the electron-richMeOtolan (2a) displayed no clear metal selectivity. Furthermore, considering that there was no significant energy difference between the Cd2+ complexes of 1 and 2b, the intended regio-effect (7- vs. 5-substituted effect) did not induce steric hindrance. Thus, the regio-effect is mainly electronic. Considering the above, 2a and 2b constitute a complete showcase in which electronic and regio-effects modulate the metal selectivity. The fluorescence titration of 2b (10 mM) with Cd2+ showed that the limit of detection (LOD) of the Cd2+-selective 2b was 158 nM in PBS (phosphate-buffered saline) (10 mM, pH 7.2) containing 50%MeOH.