"44" . "Facilitated reduction and oxidation of {[Ru(NH3)5]4(\u03BC4-TCNX)}8+ by changing from TCNX = TCNQ to TCNQF4"@en . "000308844000022" . . . "Facilitated reduction and oxidation of {[Ru(NH3)5]4(\u03BC4-TCNX)}8+ by changing from TCNX = TCNQ to TCNQF4" . . . "Rajkumar, J." . "10.1016/j.poly.2012.06.066" . . . "Polyhedron" . "Facilitated reduction and oxidation of {[Ru(NH3)5]4(\u03BC4-TCNX)}8+ by changing from TCNX = TCNQ to TCNQF4"@en . "EPR; ruthenium; HOMO-LUMO gap"@en . . "The new tetraruthenium compound {[Ru(NH3)5]4(\u03BC4-TCNQF4)}(PF6)8, TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8,-tetracyano-p-benzoquinodimethane, was studied by cyclic voltammetry, IR, UV\u2013Vis\u2013NIR and EPR spectroelectrochemistry. The better \u03C0 acceptor qualities of TCNQF4 in comparison to TCNQ cause more accessible reduction to produce {[Ru(NH3)5]4(\u03BC4-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 0.52 V, indicating a significantly diminished HOMO\u2013LUMO gap."@en . "I, P(GA203/09/0705), P(LD11086)" . "Facilitated reduction and oxidation of {[Ru(NH3)5]4(\u03BC4-TCNX)}8+ by changing from TCNX = TCNQ to TCNQF4" . "0277-5387" . "136016" . "[03B235E34752]" . "Schwederski, B." . "Fiedler, Jan" . "Kaim, W." . "The new tetraruthenium compound {[Ru(NH3)5]4(\u03BC4-TCNQF4)}(PF6)8, TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8,-tetracyano-p-benzoquinodimethane, was studied by cyclic voltammetry, IR, UV\u2013Vis\u2013NIR and EPR spectroelectrochemistry. The better \u03C0 acceptor qualities of TCNQF4 in comparison to TCNQ cause more accessible reduction to produce {[Ru(NH3)5]4(\u03BC4-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 0.52 V, indicating a significantly diminished HOMO\u2013LUMO gap." . "1" . "1"^^ . . "5"^^ . . "RIV/61388955:_____/12:00379901" . . "4"^^ . . "NL - Nizozemsko" . "RIV/61388955:_____/12:00379901!RIV13-GA0-61388955" . . . . . . . .