In this work, we report the design and synthesis of two chain-like pentanuclear cyanido-bridged complexes trans-[Ru(bpy)(μ-CN)][cis-Ru(bpy)(μ-NC)M(dppe)Cp*][PF] (M=Fe, 1; M=Ru, 2) and the electronic communication properties of their oxidized products 1 (m=6, 7, 8) and 2 (n=5, 6, 7, 8). The single-crystal X-ray diffraction analysis of 1 (m=4, 6, 7) and 2 show that 1 and 2 possess a Z-type array structure, 1 is a U-type one, and 1 exhibits both the types. The investigations indicate that both 1 and 2 show an extraordinarily strong electronic interaction between the two side Ru across the central NC-Ru-CN, leading to the formation of a fully delocalized cyanidometal Ru-Ru-Ru bridge for both three-electron oxidized states 1 and 2. Moreover, it should be noted that in 1 there exists no electronic interaction between the two terminal Fe ions. Upon substitution of Fe by Ru, however, 2 exhibits an electronic interaction between the two terminal metal ions across the trinuclear cyanidometal CN-Ru-NC-Ru-CN-Ru-NC bridge which is up to 20 Å.
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