Synthesis And Characterization Of The [ru3o(ch 3coo)6(py)2(bpe)ru(bpy)2cl](pf 6)2 Dimer

The polymetallic [Ru3O(CH3COO)6(py) 2(BPE)Ru(bpy)2Cl](PF6)2 complex (bpy = 2,2'-bipyridine, BPE = trans-1,2-bis(4-pyridil)ethylene and py = pyridine) was assembled by the combination of an electroactive [Ru3O] moiety with a [Ru(bpy)2(BPE)Cl] photoactive centre, and its structure was determined using positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS) spectrometry. The [Ru3O(CH3COO)6(py) 2(BPE)Ru(bpy)2Cl]2+ doubly charged ion of m/z 732 was mass-selected and subject to 15 eV collision-induced dissociation, leading to a specific dissociation pattern, diagnostic of the complex structure. The electronic spectra display broad bands at 409, 491 and 692 nm ascribed to the [Ru(bpy)2(BPE)] charge-transfer bands and to the [Ru 3O] internal cluster transitions. The cyclic voltammetry shows five reversible waves at -1.07 V, 0.13 V, 1.17 V, 2.91 V and -1.29 V (vs SHE) assigned to the [Ru3O]-1/0/+1/+2/+3 and to the bpy 0/-1 redox processes; also a wave is observed at 0.96 V, assigned to the Ru+2/+3 pair. 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