63767-78-2Relevant articles and documents
Dimer Crystallization Induced by Elemental Substitution in the Honeycomb Lattice of Ru1-xOsxCl3
Choi, Kwang-Yong,Hirai, Daigorou,Hiroi, Zenji,Kataoka, Kota,Lee, Seungyeol,Nishio-Hamane, Daisuke,Wulferding, Dirk,Yajima, Takeshi
, (2021/12/31)
Substitution effects of Os for Ru in α-RuCl3 are investigated in a wide composition range of 0 ≤ x ≤ 0.67 in Ru1-x-OsxCl3by X-ray and electron diffraction, magnetic susceptibility, heat capacity, and Raman spectroscopy measurements. Apart from the Kitaev physics with antiferromagnetic interactions increasing with x, a rich phase diagram is obtained, which includes an antiferromagnetic long-range order below 12K for x ≤ 0.15, a dome-shaped spin-singlet dimer phase below 130K for 0.15 ≤ x ≤ 0.40, and a magnetic short-range order for x > 0.40. A dimerization as similarly observed in α-RuCl3under high pressure occurs in the spin-singlet phase. It is suggested that Ru-Os pairs in the solid solutions tend to form dimers with short bonds and trigger the first-order transition in the presence of pseudo-threefold rotational symmetry for dimerization around a substituted Os atom only at low substitutions. This is a rare example of molecular orbital crystallization induced by elemental substitution in a highly disordered system. The short-range order at high substitutions may be related to a random-singlet state stabilized by bond disorder in the honeycomb net.
Synthesis, crystal structure, spectroscopic, and photoreactive properties of a ruthenium(II)-mononitrosyl complex
Tassé, Marine,Mohammed, Hasan S.,Sabourdy, Chloé,Mallet-Ladeira, Sonia,Lacroix, Pascal G.,Malfant, Isabelle
, p. 350 - 358 (2016/10/09)
A compound of formula [RuIICl(NO)(Cl-py)4](PF6)2, in which Cl-py is the 4-chloropyridine, has been synthesized in four steps and fully characterized. It crystallizes in the P1ˉ triclinic space group as [RuIICl(NO)(Cl-py)4](PF6)2·1.25H2O. Upon irradiation at λ?=?473?nm in the solid state, the N-bounded nitrosyl ligand (ground state GS: [RuII(NO)]) turns into O-bounded nitrosyl metastable state 1 (MS1: [RuII(ON)]). The population of the long-lived metastable RuII(ON) isomer is equal to 27% on powder samples, therefore 3 times less than that of the parent [RuIICl(NO)(py)4](PF6)2derivative. Spectroscopy and TD-DFT studies are proposed to find a rational for this difference at the molecular level, which is tentatively related to different UV–visible spectra in the metastable RuII(ON) isomer. Surprisingly, and while the switching efficiency of [RuIICl(NO)(Cl-py)4](PF6)2appears relatively modest, its capability for releasing the biologically active nitric oxide (NO[rad]) radical under irradiation in solution is find to be about 100 times that of the [RuIICl(NO)(py)4](PF6)2derivative.
Synthesis and characterization of rigid +2 and +3 heteroleptic dinuclear ruthenium(II) complexes
Alston,Kobayashi,Younts,Poler
, p. 2696 - 2702 (2011/01/05)
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.
