Synthesis and characterization of copper(II) dithiocarbamate complexes involving pyrrole and ferrocenyl moieties and their utility for sensing anions and preparation of copper sulfide and copper–iron sulfide nanoparticles

Abstract

Bis(N‐(pyrrol‐2‐ylmethyl)‐N‐butyldithiocarbamato‐S,S′)copper(II) (1), bis(N‐(pyrrol‐2‐ylmethyl)‐N‐(2‐phenylethyl)dithiocarbamato‐S,S′)copper(II) (2), bis(N‐methylferrocenyl‐N‐(2‐phenylethyl)dithiocarbamato‐S,S′)copper(II) (3) and bis(N‐furfuryl‐N‐methylferrocenyldithiocarbamato‐S,S′)copper(II) (4) were prepared and characterized using elemental analysis and infrared and UV–visible spectroscopies. X‐ray diffraction (XRD) studies on 3 show that each copper centre adopts the square planar geometry by the coordination of four sulfur atoms of the metalloligand N‐methylferrocenyl‐N‐(2‐phenylethyl)dithiocarbamate. The CuS distances are symmetrical and are in the range 2.293–2.305 Å. The supramolecular architecture in complex 3 is sustained in the solid state by CH⋅⋅⋅π, CH⋅⋅⋅S, Fe⋅⋅⋅Fe and H⋅⋅⋅H interactions. Density functional theory calculations were carried out for 3. Anion (F−, Cl−, Br− and I−) binding studies with complex 1 were performed using cyclic voltammetry. Copper sulfide, copper–iron sulfide‐1 and copper–iron sulfide‐2 nanoparticles were prepared from complexes 2, 3 and 4, respectively, and they were characterized using powder XRD, transmission electron microscopy (TEM) and energy‐dispersive X‐ray, UV–visible, photoluminescence and infrared spectroscopies. TEM images of copper–iron sulfide‐1 and copper–iron sulfide‐2 reveal that the particles are spherical and oval shaped, respectively. Photocatalytic activities of as‐prepared nanoparticles were studied by decolourization of methylene blue and rhodamine‐B under UV light. It was found that copper–iron sulfide degrades methylene blue and rhodamine‐B much better than does copper sulfide.