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Chain-Like Pentanuclear Complexes: Syntheses, Crystal Structures and Long-Range Electronic Interactions of
Xiao-Lin Liu1,2, Yi Li1, Hao Wang1
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P. R. China.
Abstract:
In this work, we report the design and synthesis of two chain-like pentanuclear cyanido-bridged complexes trans-[Ru(bpy)2(μ-CN)2][cis-Ru(bpy)2(μ-NC)M(dppe)Cp*]2[PF6]4 (M=Fe, 14+; M=Ru, 24+) and the electronic communication properties of their oxidized products 1m+ (m=6, 7, 8) and 2n+ (n=5, 6, 7, 8). The single-crystal X-ray diffraction analysis of 1m+ (m=4, 6, 7) and 24+ show that 14+ and 24+ possess a Z-type array structure, 17+ is a U-type one, and 16+ 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 17+ and 27+. 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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