Abstract
The reaction of a paddlewheel-type diruthenium(II, II) complex, [Ru2(2,3,5,6-F4-PhCO2)4(MeOH)2] (2,3,5,6-F4-PhCO2−=2,3,5,6-tetrafluorobenzoate), with acridine (acr) produces an acridine-capped discrete compound, [Ru2(2,3,5,6-F4-PhCO2)4(acr)2]·toluene (1). The Ru–Ru and Ru–Nax (Nax=axial N atom of acridine) bond lengths are 2.3087(5)Å and 2.450Å (average), respectively, and the average Ru–Oeq length (Oeq=carboxylate oxygen atom) is 2.074Å, indicating an oxidation state of [Ru2II,II]. The reaction of 1 with 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) leads to a π-stacked aggregation with a formulation of [Ru2(2,3,5,6-F4-PhCO2)4(acr)2]·TCNQ·2CH2Cl2 (1-TCNQ). Even in a donor/acceptor aggregated system of 1-TCNQ, the Ru–Ru and Ru–Nax bond lengths are 2.3072(9)Å and 2.443(3)Å, respectively, similar to those of 1, and the average Ru–Oeq length is 2.072Å, which replies an oxidation state of [Ru2II,II] as well as the case in 1. Indeed, the charge ρ of the TCNQ moiety in 1-TCNQ was evaluated to be almost zero (ρ=−0.063), and the infrared spectra of 1-TCNQ agree with the neutral state of compound. The DFT calculations for 1 have revealed that its HOMO (HOMO[Ru2]) is associated with δ∗ orbital of Ru–Ru bond and lies at −5.088eV, which is very close to the LUMO level for TCNQ (LUMOTCNQ with −5.122eV). The gap between the HOMO[Ru2] and LUMOTCNQ levels could be insufficient to induce CT in 1-TCNQ.
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