Abstract
The new tetraruthenium compound {[Ru(NH3)5]4(μ4-TCNQF4)}(PF6)8, TCNQF4=2,3,5,6-tetrafluoro-7,7,8,8,-tetracyano-p-benzoquinodimethane, was studied by cyclic voltammetry, IR, UV–Vis–NIR and EPR spectroelectrochemistry. The better π acceptor qualities of TCNQF4 in comparison to TCNQ cause more accessible reduction to produce {[Ru(NH3)5]4(μ4-TCNQF4)}7+ with enhanced metal contribution to the singly occupied MO and low-energy shifted IR vibrational and NIR electronic absorptions. However, the two-electron oxidation to the (10+) ion is also facilitated. The reason is seen in a more metal-centered oxidation for the TCNQF4 complex while the previously studied TCNQ analogue is assumed to undergo a higher degree of oxidation at the bridging ligand. As a result, the title species has a redox potential range of only 0.52V, indicating a significantly diminished HOMO–LUMO gap.
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