Substituted pyridazines as ligands in homoleptic (fac and mer) and heteroleptic Ru(ii) complexes

Abstract

This article reports the preparation of a range of phenyl, pyridyl and pyrazinyl substituted pyridazinesvia the inverse electron demand [2 + 4] Diels–Alder reaction between 3,6-di(2-pyridyl)-1,2,4,5-tetrazines (bptz) and 3,6-di(2-pyrazinyl)-1,2,4,5-tetrazines (bpztz) and suitable dienophiles including acenaphthalene. The resulting polyaromatic compounds vary systematically in the number of aromatic substituents and the number and position of N-heteroatoms. For four of these compounds, the effect of the molecular changes on the solid-state structures were investigated using single crystal X-ray crystallography. The pyridazines were used as bidentate ligands in {M(II)(bipy)₂} and tris(homoleptic) complexes (M = Fe, Ru). The optical and electrochemical properties of these complexes reflect the electron accepting character of the new ligands. The facial and meridional isomers of the tris complexes could be separated by column chromatography (on silica), thus allowing a spectral comparison of their absorption and emission properties. The solid-state structures of several of the metal complexes are discussed, including that of the facial isomer of the trisRu(II) complex of 3,6-bis(2-pyridyl)-4,5-bis(4-pyridyl)pyridazine—a potential preformed geometric motif for the predirected construction of supramolecular assemblies.