Development and application of redox-active cyclometallating ligands based on W() alkyne complexes

The assembly of dinuclear complexes with the ultimate smallest ditopic ligands based on side-on complexes of methyl substituted alkynes is presented. In fact, the coordination of Ru( ii ) and Ir( iii ) by a W alkyne complex based cyclometallating metalla-ligand causes close intermetallic electronic cooperation, which substantially changes the electrochemical and photophysical properties of the single isolated moieties. The preparative assembly and electrochemical and photophysical behavior of di- and tetranuclear complexes held together by minimalist ditopic ligands based on 1-phosphine- or 1-pyridine-substituted prop-1-ynes are presented.