TTF-Annulated Phenanthroline and Unexpected Oxidative Cleavage of the CC Bond in Its Ruthenium(II) Complex

Tetrathiafulvalene (TTF) and 1,10-phenanthroline have been fused together via a simple and efficient synthetic procedure that provides a new bidentate ligand, 4′,5′-ethylenedithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline (EDT-TTF-phen, 1). Its ruthenium(II) complex exhibits a unique packing of TTF subunits in the solid state. In an acetonitrile solution, [Ru(bpy)2(1)](PF6)2 undergoes facile oxidative cleavage of the CC double bond, which cannot be observed in the dark or under anaerobic conditions. This points to the photocatalytic role played by the ruthenium(II) chromophore in this conversion.