Synthesis and characterization of binuclear ruthenium vinyl complexes: effect of transannular substituents on their optoelectronic properties

A series of substituted dithia[3.3]paracyclophane-bridged binuclear ruthenium vinyl complexes have been synthesized by insertion reactions of [RuHCl(CO)(PPh3)3] with the appropriate dialkynes. The products have been characterized by physico-chemical and spectroscopic methods. In addition, the structure of one complex has been determined by X-ray crystallography. Electrochemical studies have shown that all of the substituted complexes exhibit smaller ΔE values relative to the unsubstituted complex. Photoluminescence studies indicated that all of the examined substituent groups act as “quenchers,” except for the methoxy group.