Luminescence Color and Intensity Changes of Nitridorhenium(V) Complexes Induced by Protonation/Deprotonation on the Bidentate Azolylpyridine Ligands

Abstract

Tricyanidonitridorhenium­(V) complexes with azolylpyridines, namely, [ReN­(CN)3(H–N2py)]− (1-H, H–N2py = 2-(3-pyrazolyl)­pyridine) and [ReN­(CN)3(L)]2– (2-a, L = 2-[1,2,3]-triazol-4-yl-pyridine anion (N3py–), and 3-a, that is, L = 2-(tetrazol-5-yl)-pyridine anion (N4py–)), were newly synthesized and characterized. The structures of the new complexes were determined by single-crystal X-ray analysis. The 1-H complex includes two geometrical isomers in which an isomer is the conformation with the pyridyl (py) and pyrazolyl (pyrz) moieties of H–N2py occupying the trans site to the nitrido (the ax site) and the trans site to the cyanido (the eq site), respectively, in a bidentate fashion; the other isomer is the py and pyrz moieties coordinated to the eq and ax sites. In 2-a and 3-a, the triazolyl (trz) and tetrazoly (tetrz) moieties in N3py– and N4py– occupy the eq site, and the py moieties in N3py– and N4py– coordinate to the ax site. The complex 1-H is deprotonated upon the addition of 1,8-diazabicyclo[5.4.0]­undec-7-one or NaOH to produce [ReN­(CN)3(N2py)]2– (1-a), and 2-a is protonated upon the addition of p-toluene sulfonic acid (TsOH) to give [ReN­(CN)3(H–N3py)]− (2-H) in DMSO. The protonation reaction does not occur for 3-a with TsOH in DMSO. All the complexes show one-electron redox waves of the Re­(VI)/Re­(V) and azolylpyridine ligand-centered processes in 0.1 M (n-C4H9)4NPF6–DMSO. All the complexes exhibit photoluminescence in DMSO and in the crystalline phase at 296 K. The emissive excited states of the complexes in DMSO were assigned to MLCT with a spin triplet nature. The emission band shifts to shorter and longer wavelengths upon protonation and deprotonation of the coordinated azolylpyridines, respectively. The emission color and intensity changes of 2-H and 2-a in the presence of acidic and basic vapors were investigated.