Coordination of Distal Carboxylate Anion Alters Metal Ion Specific Binding in Imidazo[1,2-a]pyridine Congeners.

Imidazo[1,2-a]pyridine derivatives have excellent potential for chelation with transition metal ions. Two new imidazo[1,2-a]pyridine-8-carboxylates were synthesized and characterized by ¹H NMR, ¹³C NMR, HRMS, and single crystal-XRD techniques. Methyl carboxylate (probe 1) turns on fluorescence upon coordination with Zn²⁺, while sodium carboxylate (probe 2) turns off its fluorescence upon coordination with Co²⁺ or Cu²⁺ ions present in aqueous acetonitrile medium. ¹³C NMR study revealed that the change in metal ion specific binding was due to the involvement of carboxylate anion in complex formation with Co²⁺ or Cu²⁺ ions. The carboxylate anion at 8-position also enhanced the sensitivity of detection of probe 2 by an order of magnitude (detection limits: 3.804 × 10^–7 M, probe 1/Zn²⁺; 0.420 × 10^–7 M, probe 2/Co²⁺ and 0.304 × 10^–7 M, probe 2/Cu²⁺). The detection limits of probes 1 and 2 comply well with the World Health Organization (WHO) and US Environmental Protection Agency (US-EPA) guidelines for detection of heavy metal ions present in drinking water and ground water. Both the probes form a 1:1 complex with Zn²⁺, Co²⁺ or Cu²⁺, and the stoichiometry was verified by Job plot and ESI-mass analysis. The sensing mechanism is explained using ¹³C NMR experiments, ESI-mass analytical data and theoretical DFT calculations. The suitability of probes 1 and 2 for on-site detection and quantitative determination of Zn²⁺, Co²⁺ and Cu²⁺ ions present in biological, environmental and industrial samples is demonstrated. In addition, both 1 and 2 are used for detection of intracellular contamination of Zn²⁺, Co²⁺ or Cu²⁺ ions in onion epidermal cells. [ABSTRACT FROM AUTHOR]