A new biphenol-dipicolylamine based ligand and its dinuclear Zn2+ complex as fluorescent sensors for ibuprofen and ketoprofen in aqueous solution

Abstract

In this work, the study of the new ligand 3,3′-bis[N,N-bis(pyridine-2-ylmethyl)aminomethyl]-2,2′-dihydroxybiphenyl (L) is reported, where a central 2,2′-biphenol (BPH) fluorophore was functionalized at 3,3′-positions with two dipicolylamine (DPA) side arms as receptor units. Following the synthesis and full chemical–physical characterization, the acid–base and Zn²⁺-coordination abilities of L were investigated through a combination of potentiometric, UV-Vis, fluorescence, NMR, XRD and DFT measurements. The optical properties of the ligand turned out to be strongly dependent on the pH, being straightforwardly associated with the protonation state of the BPH moiety, whereas its peculiar design allowed to form stable mono and dinuclear Zn²⁺ complexes. In the latter species, the presence of two Zn²⁺ ions coordinatively unsaturated and placed at close distance to each other, prompted us to test their usefulness as metallo-receptors for two environmental pollutants of great relevance, ibuprofen and ketoprofen. Potentiometric and fluorescence investigations evidenced that these important non-steroidal anti-inflammatory drugs (NSAIDs) are effectively coordinated by the metallo-receptors and, of relevance, both the stability and the fluorescence properties of the resulting ternary adducts are markedly affected by the different chemical architectures of the two substrates. This study aims at highlighting the promising perspectives arising from the use of polyamino phenolic ligands as chemosensors for H⁺/Zn²⁺ and other additional anionic targets in their metal-complexed forms.