Abstract
The reaction of a paddlewheel-type diruthenium(II, II) complex, [Ru 2(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-N ax (Nax = axial N atom of acridine) bond lengths are 2.3087(5) Å and 2.450 Å (average), respectively, and the average Ru-Oeq length (Oeq = carboxylate oxygen atom) is 2.074 Å, 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-F 4-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 2.072 Å, 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 -5.088 eV, which is very close to the LUMO level for TCNQ (LUMOTCNQ with -5.122 eV). The gap between the HOMO[Ru2] and LUMOTCNQ levels could be insufficient to induce CT in 1-TCNQ.
Original language | English |
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Pages (from-to) | 1213-1218 |
Number of pages | 6 |
Journal | Polyhedron |
Volume | 52 |
DOIs | |
Publication status | Published - 2013 Mar 22 |
Externally published | Yes |
Keywords
- Aggregating form
- Charge-transfer complex
- DFT calculation
- Paddlewheel-type diruthenium(II, II) complex
- TCNQ
- π-Stacking
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry