10049-08-8Relevant articles and documents
Synthesis and characterization of rigid +2 and +3 heteroleptic dinuclear ruthenium(II) complexes
Alston,Kobayashi,Younts,Poler
, p. 2696 - 2702 (2010)
Synthesis and characterization of the dinuclear ruthenium coordination complexes with heteroleptic ligand sets, [Cl(terpy)Ru(tpphz)Ru(terpy)Cl](PF 6)2 (7) and [(phen)2Ru(tpphz)Ru(terpy)Cl] (PF6)3 (8), are reported. Both structures contain a tetrapyrido[3,2-α:2′,3′-c:3″,2″-h:2″, 3″-j]phenazine (tpphz) (6) ligand bridging the two metal centers. Complex 7 was obtained via ligand exchange between, RuCl2(terpy)DMSO (5) and a tpphz bridge. Complex 8 was obtained via ligand exchange between, [Ru(phen)2tpphz](PF6)2 (4) and RuCl 2(terpy)DMSO (5). Metal-to-ligand-charge-transfer (MLCT) absorptions are sensitive to ligand set composition and are significantly red-shifted due to more electron donating ligands. Complexes 7-9 have been characterized by analytical, spectroscopic (IR, NMR, and UV-Vis), and mass spectrometric techniques. The electronic spectral properties of 7, 8, and [(phen) 2Ru(tpphz)Ru(phen)2](PF6)4 (9), a previously reported +4 analog, are presented together. The different terminal ligands of 7, 8, and 9 shift the energy of the MLCT and the π-π* transition of the bridging ligand. These shifts in the spectra are discussed in the context of density functional theory (DFT). A model is proposed suggesting that low-lying orbitals of the bridging ligand accept electron density from the metal center which can facilitate electron transfer to nanoparticles like single walled carbon nanotubes and colloidal gold.
Hill, M. A.,Beamish, F. E.
, p. 4855 - 4856 (1950)
About trihalides with TiI3 chain structure: Proof of pair forming of cations in β-RuCl3 and RuBr3 by temperature dependent single crystal X-ray analyses
Hillebrecht,Ludwig,Thiele
, p. 2199 - 2204 (2004)
Single-crystal X-ray studies on β-RuCl3 and RuBr 3 at different temperatures verified, that both compounds are dimorphic and show reversible phase transitions at 206 K resp. 384 K. In the HT-forms the Aristo-type of the hexagonal TiI3-structure with space group P63/m c m (Z = 2, β-RuCl3 at 293(2) K: a = 6.121(2) A, c =5.655(2) A, RuBr3 at 423(3) K: 6.5215(12) A, c = 5.8851(13) A) has been found, in the LT-forms the RuBr 3-type structure, an orthorhombic distorted variant with space group Pmmn (Z = 4, β-RuCl3 at 170(3) K: a = 10.576(2) A, b = 5.634(1) A, c = 6.106(1) A, RuBr3 at 293(2) K: a =11.2561(16) A, b = 5.8725(12) A, c = 6.4987(9) A). A hexagonal closest packing of X- anions forms the basis of an arrangement of infinite chains with face-connected [RuX6/2] octahedra. While in the chains of the hexagonal HT-forms the Ru-Ru-distances are identical (d(Ru-Ru) = 2.8275(10) A for β-RuCl3, d(Ru-Ru) = 2.9425(6) A for RuBr 3), in the orthorhombic structures the chains are distorted through pairing of the ruthenium(III) atoms (d(Ru-Ru) = 2.6328(14) A / 3.0010(15) A for β-RuCl3 at 170(3) K, d(Ru-Ru) = 2.765(1) A / 3.108(1) A for RuBr3 at 293(2) K). The hexagonal metric with a/c= √3 holds also for the orthorhombic LT-forms. Large crystals and the final products of the phase transition from HT- to LT-forms are pseudomerohedral twins of three twin domains with nearly equal amounts complicating proof and analysis of the LT-forms.
Electronic properties of the narrow-band material α-RuCl3
Pollini
, p. 12769 - 12776 (1996)
X-ray angle-integrated and ultraviolet angle-resolved photoemission spectra of the low-spin compound t2g5 α-RuCl3 show that Ru 4d and Cl 3p states contribute to the valence-band structure of this magnetic material. The energy distribution curves measured along the azimuthal directions Γ-M′-π and Γ-K-M using He I radiation indicate an uppermost nearly dispersionless structure of Ru 4d origin, and two dispersive features obtained from Cl 3p-derived bands. The photoemission results, together with the optical and magnetic properties described by ligand-field theory, support the view of localized 4d states forming a very narrow Ru 4d band in the vicinity of the Fermi energy. The main 4d emission structure has been thus assigned to 4d4 unscreened hole states, where the band gap corresponds to intersite d-d transitions, and α-RuCl3 can be classified as a Mott-Hubbard compound in consideration of its electronic and magnetic characteristics. The inconsistency between the photoemission results and the transport properties, describing this material as a conventional band-gap semiconductor, is finally discussed.
Influence of solvent on aromatic interactions in metal tris-bipyridine complexes
Breault, Gloria A.,Hunter, Christopher A.,Mayers, Paul C.
, p. 3402 - 3410 (2007/10/03)
The conformational properties of a series of iron(II) and ruthenium(II) tris-bipyridine complexes have been investigated in a range of solvents. The complexes are equipped with pendant aromatic esters attached by flexible aliphatic linkers, and aromatic i