Donor/acceptor neutral aggregation of a paddlewheel-type [Ru 2II,II] complex and TCNQ

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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 languageEnglish
Pages (from-to)1213-1218
Number of pages6
JournalPolyhedron
Volume52
DOIs
Publication statusPublished - 2013 Mar 22
Externally publishedYes

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

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