Anion recognition by 2,2′-binaphthalene derivatives bearing urea and thiourea groups at 8- and 8′-positions by UV–vis and fluorescence spectroscopies

Abstract

Synthesis and anion recognition properties of 2,2′-binaphthalene derivatives bearing two thiourea ( 1) and urea ( 2) groups at 8- and 8′-positions were studied. The structure of receptor 1 was determined by X-ray crystallography. UV–vis spectra of the receptors showed characteristic changes around 300–400 nm through isosbestic points upon the addition of biologically relevant anions such as acetate, dihydrogenphosphate, and chloride in MeCN and DMSO due to restriction of the rotation around the single bond connecting two naphthyl moieties by cooperative guest binding of two recognition sites. Job’s plots showed 1:1 complexation for guest anions. The fluorescence quantum yields of free form of 1 and 2 in MeCN were determined to be 0.021 and 0.57, respectively. The fluorescence intensities of the receptors diminished upon the addition of anions in MeCN. The association constants of receptors 1 and 2 were one or two orders of magnitude greater than the corresponding monothiourea and urea receptors 3 and 4 indicating cooperative hydrogen bonding with guest anions. The selectivity trends of association of anions were F −>AcO −>H 2PO 4 −>Cl −>>HSO 4 −≈NO 3 −≈Br −≈I − for 1, and F −>AcO −≈Cl −>H 2PO 4 −>Br −>HSO 4 −>I −≈NO 3 − for 2. Receptor 2 showed remarkable Cl − selectivity presumably owing to suitable orientation for effective hydrogen bond formation with Cl −.