Ligand-centered redox in nickel(II) complexes of 2-(arylazo)pyridine and isolation of 2-pyridyl-substituted triaryl hydrazines via catalytic N-arylation of azo-function.

Abstract

A series of nickel complexes of 2-(arylazo)pyridine have been synthesized, and the precise structure and stoichiometry of the complexes are controlled by the use of different metal precursors. Molecular and electronic structures of the isolated complexes are scrutinized thoroughly by various spectroscopic techniques, single crystal X-ray crystallography, and density functional theory (DFT). Two different classes of Ni(II) complexes are identified where the ligands bind as neutral or anion radicals in the respective metal complexes. These are shown to be chemically interconvertible, and their characterization confirmed that the redox series is entirely ligand-centered without affecting the bivalent oxidation state of the metal ion. An efficient method of Ni(II) catalyzed N-arylation of 2-(arylazo)pyridine substrates has been elaborated. The chemical reactions have led to isolation of strongly fluorescent 2-pyridyl-substituted hydrazine derivatives, which have been characterized thoroughly. Three-dimensional X-ray structure of a hydrazine molecule, 2-(2-(naphthalen-1-yl)-2-phenylhydrazinyl)pyridine, is reported. Isolated hydrazines satisfy all the prerequisites of an ideal dye with moderate absorptive property, large Stokes shift, high quantum yields, and high photostability.