Ferrocenyl–triazole complexes and their use in heavy metal cation sensing

Abstract

Complexes tris((1-ferrocenyl-1H-1,2,3-triazol-4-yl)methyl)amine (3), bis((1-ferrocenyl-1H-1,2,3-triazol-4-yl)methyl)amine (6), bis((1-ferrocenyl-1H-1,2,3-triazol-4-yl)methyl)ether (7), and 1-ferrocenyl-1H-1,2,3-triazol-4-yl)methanamine (9) were synthesized using the copper-catalyzed click reaction. Complexes 3, 6, 7, and 9 were characterized using NMR (¹H and ¹³{¹H}) and IR spectroscopy, elemental analysis, and mass spectrometry. Structures of 3, 7, and 9 in the solid state were determined using single-crystal X-ray diffraction. It was found that the triazole rings were planar and slightly twisted with respect to the cyclopentadienyl groups attached to them. Chains and 3D network structures were observed due to the presence of π⋯π and C–H⋯N interactions between the cyclopentadienyl and triazole ligands. A reversible redox behavior of the Fc groups between 239 and 257 mV with multicycle stability was characteristic for all the compounds, revealing that the electrochemically generated species Fc⁺ remained soluble in dichloromethane. Electrochemical sensor tests demonstrated the applicability of all the complexes to enhance the quantification sensing behavior of the screen-printed carbon electrode (SPCE) toward Cd²⁺, Pb²⁺, and Cu²⁺ ions.