Synthesis, Photophysical Properties, and Metal-Ion Recognition Studies of Fluoroionophores Based on 1-(2-Pyridyl)-4-Styrylpyrazoles

Jessica Orrego-Hernández; Justo Cobo; Jaime Portilla

doi:10.1021/acsomega.9b02796

Synthesis, Photophysical Properties, and Metal-Ion Recognition Studies of Fluoroionophores Based on 1-(2-Pyridyl)-4-Styrylpyrazoles

ACS Omega. 2019 Sep 26;4(15):16689-16700. doi: 10.1021/acsomega.9b02796. eCollection 2019 Oct 8.

Authors

Jessica Orrego-Hernández¹, Justo Cobo², Jaime Portilla¹

Affiliations

¹ Bioorganic Compounds Research Group, Department of Chemistry, Universidad de los Andes, Carrera 1 No. 18A-10, 111711 Bogotá, Colombia.
² Departamento de Química Inorgánica y Orgánica Campus las Lagunillas, Universidad de Jaén, 23071 Jaén, Spain.

Abstract

A convenient access toward novel fluoroionophores based on 1-(2-pyridyl)-4-styrylpyrazoles (PSPs) substituted at position 3 with donor or acceptor aryl groups is reported. The synthesis proceeds in two steps: the first one via Wittig olefination of the appropriate 4-formylpyrazole and then Mizoroki-Heck coupling to yield the desired products in an overall yield of up to 69%. Photophysical properties of products (4-styryl) and their intermediates (4-vinyl) were explored, finding that they have strong blue-light emission with high quantum yields (up to 66%) due to ICT phenomena. The 3-phenyl PSP was studied as a turn-off fluorescent probe in metal ion sensing, finding a high selectivity to Hg²⁺ (LOD = 3.1 × 10^-7 M) in a process that could be reversed with ethylenediamine. The sensing mechanism and binding mode of the ligand to Hg²⁺ were established by HRMS analysis and ¹H NMR titration tests.