Photoredox vs. energy transfer in a Ru(II)-Fe(II) supramolecular complex built with an heteroditopic bipyridine-terpyridine ligand

ZA trinuclear [{Ru-II(bpy)(2)(bpy-terpy)}(2)Fe-II](6+) complex (I) in which a Fe-II-bis-terpyridine-like centre is covalently linked to two Ru-II-tris-bipyridine-like moieties by a bridging bipyridine-terpyridine ligand has been synthesised and characterised. Its electrochemical, photophysical and photochemical properties have been investigated in CH3CN and compared with those of mononuclear model complexes. The cyclic voltammetry of (I) exhibits, in the positive region, two successive reversible oxidation processes, corresponding to the Fe-III/Fe-II and Ru-III/Ru-II redox couples. These systems are clearly separated (Delta E-1/2 = 160 mV), demonstrating the lack of an electronic connection between the two subunits. The two oxidized forms of the complex, [{Ru-II(bpy)(2)(bpy-terpy)}(2)Fe-III](7+) and [{Ru-III(bpy)(2)(terpy-bpy)}(2)Fe-III](9+), obtained after two successive exhaustive electrolyses, are stable. (I) is poorly luminescent, indicating that the covalent linkage of the Ru-III-tris-bipyridine to the Fe-II-bis-terpyridine subunit leads to a strong quenching of the Ru-II* excited state by energy transfer to the Fe-II centre. Luminescence lifetime experiments show that the process occurs within 6 ns. The nature of the energy transfer process is discussed and an intramolecular energy exchange is proposed as a preferable deactivation pathway. Nevertheless this energy transfer can be efficiently quenched by an electron transfer process in the presence of a large excess of the 4-bromophenyl diazonium cation, playing the role of a sacrificial oxidant. Finally complete photoinduced oxidation of (I) has been performed by continuous photolysis experiments in the presence of a large excess of this sacrificial oxidant. The comparison with a mixture of the corresponding mononuclear model complexes has been made.