When organophosphorus ruthenium complexes covalently bind to ruthenium nanoparticles to form nanoscale hybrid materials.

A hybrid material made of mononuclear organophosphorus polypyridyl ruthenium complexes covalently bonded to ruthenium nanoparticles has been synthesized via a one-pot organometallic procedure and finely characterized. These results open new avenues to access unique hybrid transition metal nanomaterials.

Phosphoryl group as a strong σ-donor anionic phosphine-type ligand: a combined experimental and theoretical study on long-lived room temperature luminescence of the [Ru(tpy)(bpy)(Ph2PO)]+ complex.

A phosphoryl Ru(II) polypyridyl complex was prepared in a one-pot process. Theoretical analysis suggests that the phosphoryl ligand may be viewed as a strong σ-donor anionic phosphine L-type ligand. State-of-the-art free-energy profile calculations on the excited states demonstrate that both favorable thermodynamic and kinetic factors are responsible for the remarkable room temperature luminescence properties of the phosphoryl complex.

Theoretical investigation of phosphinidene oxide polypyridine ruthenium(II) complexes: toward the design of a new class of photochromic compounds.

A DFT-based computational study performed in the gas phase and in acetonitrile on polypyridine ruthenium isomer complexes [Ru(tpy)(bpy)(POPh)](2+) and [Ru(tpy)(bpy)(OPPh)](2+) (bpy = 2,2'-bipyridine, tpy = 2,2':6',2″-terpyridine, Ph = phenyl) predicts that they constitute a prototype for a new family of inorganic photochromic systems. The two isomers are found to absorb in different spectral regions to excited states that are connected adiabatically through a thermodynamically and kinetically favorable triplet potential energy profile. Nonadiabatic routes were identified and shown to be preferable over the adiabatic mechanism. The reverse isomerization reaction is found to be achievable only thermally. The current predictive work will be of prime importance to experimentalists for the design of new inorganic phosphorus-based compounds with attractive photochromic properties.

Bis(2,2'-bipyridine)[1,9-bis(diphenylphos-phanyl)-1,2,3,4,6,7,8,9-octahydropyrim-ido[1,2-a]pyrimidin-5-ium]ruthenium(II) hexa-fluorido-phosphate dibromide di-chloro-methane disolvate monohydrate.

In the cation of the title complex, [Ru(C31H32N3P2)(C10H8N2)2](PF6)(Br)2·2CH2Cl2·H2O, the ruthenium ion is coordinated in a distorted octa-hedral geometry by two 2,2'-bi-pyridine (bpy) ligands and a chelating cationic N-di-phenyl-phosphino-1,3,4,6,7,8-hexa-hydro-2-pyrimido[1,2-a]pyrimidine [(PPh2)2-hpp] ligand. The tricationic charge of the complex is balanced by two bromide and one hexa-fluorido-phosphate counter-anions. The compound crystallized with two mol-ecules of di-chloro-methane (one of which is equally disordered about a Cl atom) and a water mol-ecule. In the crystal, one of the Br anions bridges two water mol-ecules via O-H⋯Br hydrogen bonds, forming a centrosymmetric diamond-shaped R (4) 2(8) motif. The cation and anions and the solvent mol-ecules are linked via C-H⋯F, C-H⋯Br, C-H⋯Cl and C-H⋯O hydrogen bonds, forming a three-dimensional network.

Chlorido(η(6)-N (2)-diphenylphosphanyl-N (1),N (1)-diisopropyl-4-methoxybenz-amidine-κP)(triphenylphosphane-κP)ruthenium(II) trifluoromethansulfonate acetone disolvate.

In the title compound, [RuCl(C18H15P)(C26H31N2OP)](CF3O3S)·2C3H6O, the Ru(II) ion is coordinated in a three-legged piano stool, half-sandwich-type geometry by a chlorido ligand, a tri-phenyl-phosphine and a tethered η(6)-(phenyl-p-O-meth-oxy) κ(1)-P N-di-phenyl-phosphino N'-diisopropyl amidine ligand charge-balanced by a trifluormethansulfonate counter-anion. The η(6)-coordination mode of the arene incorporated into the structure was generated in situ after addition of methyl tri-fluoro-methane-sulfonate to the neutral η(5)-arene tethered precursor complex [RuCl(PPh3)(η(5):κ(1)-OC6H4C(NiPr2)=N-PPh2)] in di-chloro-methane solution.

Can a functionalized phosphine ligand promote room temperature luminescence of the [Ru(bpy)(tpy)]2+ core?

Unexpected room temperature luminescence is observed and rationalized by highly challenging excited state calculations for a functionalized phosphine ligand coordinated on the [Ru(bpy)(tpy)](2+) core.

Theoretical investigation on the photophysical properties of model ruthenium complexes with diazabutadiene ligands [Ru(bpy)(3-x)(dab)(x)](2+) (x = 1-3).

In this study we report a theoretical comparative study of some photophysical properties in the [Ru(bpy)(3-x)(dab)(x)](2+) (x = 0-3) series. Density functional theory calculations, validated by highly correlated ab initio benchmark calculations, were used to investigate the absorption and emission properties of the complexes with x = 1-3. The presence of a 1,4-diaza-1,3-butadiene (dab) ligand dramatically changes these properties because of the strong π-acceptor character of this ligand. As a result, comparing to the reference [Ru(bpy)(3)](2+) complex previously studied, we observed (i) a strong red-shift of the maximum of the absorption band, (ii) a strong decrease of the emission energy of the lowest triplet metal-to-ligand charge transfer state, with all the [Ru(bpy)(3-x)(dab)(x)](2+) (x = 1-3) complexes luminescent in the near-infrared region, while [Ru(bpy)(3)](2+) emits in the visible region, and (iii) the triplet metal-centered states become inaccessible in all the [Ru(bpy)(3-x)(dab)(x)](2+) (x = 1-3) complexes. Consequently, these complexes could be potential candidates for infrared light-emitting diodes and probes.

Luminescent ruthenium-polypyridine complexes & phosphorus ligands: anything but a simple story.

This tutorial review presents an exhaustive picture of the luminescence studies that have been undertaken on ruthenium(ii) complexes bearing polypyridine and phosphorus(iii) ligands. The introduction of phosphorus to the Ru coordination sphere has multiple consequences on the nature and energy of the various excited states involved, but it does not necessarily rule out room temperature emission.

Broad HOMO-LUMO gap tuning through the coordination of a single phosphine, aminophosphine or phosphite onto a Ru(tpy)(bpy)2+ core.

The synthesis of new ruthenium(II) terpyridine bipyridine complexes bearing a phosphorus(III) ligand is presented. The steric and electronic properties of the phosphorus ligand were varied using aminophosphines, alkyl and aryl phosphites and the bulky tri(isopropyl)phosphine. All complexes were characterized by multi-nuclear NMR spectroscopy, mass spectrometry and X-ray diffraction analysis. The electronic properties of the complexes were probed by cyclic voltammetry, absorption and luminescence spectroscopy. The complexes do not show luminescence at room temperature, whereas at 77 K in an alcoholic matrix, emission is observed in the range 600-650 nm with lifetimes of 3.5-5.5 micros, originating from 3MLCT states. The MLCT transition spans over 65 nm, which corresponds to a variation of 0.4 eV in the HOMO-LUMO gap. The oxidation potential of the ruthenium varies over a broad range of 290 mV, from +1.32 V vs. SCE with L = PiPr3 to +1.61 V vs. SCE with L = P(OPh)3. This range is unprecedented upon the variation of a single monodentate ligand coordinated by the same heteroatom in the same oxidation and charge states. This work underlines the specific capacity of phosphorus in bringing up a large variety of electronic properties by changing its substituents.

Vibrational progressions in the valence ionizations of transition metal hydrides: evaluation of metal-hydride bonding and vibrations in (eta(5)-C(5)R(5))Re(NO)(CO)H [R = H, CH(3)].

The first examples of vibrational structure in metal-ligand sigma-bond ionizations are observed in the gas-phase photoelectron spectra of CpRe(NO)(CO)H and CpRe(NO)(CO)H [Cp = eta(5)-C(5)H(5), Cp = eta(5)-C(5)(CH(3))(5)]. The vibrational progressions are due to the Re-H stretch in the ion states formed by removal of an electron from the predominantly Re-H sigma-bonding orbitals. A vibrational progression is also observed in the corresponding ionization of the deuterium analogue, CpRe(NO)(CO)D, but with lower vibrational energy spacing as expected from the reduced mass effect. The vibrational progressions in these valence ionizations are directly informative about the nature of the metal-hydride bonding and electronic structure in these molecules. Franck-Condon analysis shows that for these molecules the Re-H or Re-D bond lengthens by 0.25(1) A when an electron is removed from the Re-H or Re-D sigma-bond orbital. This bond lengthening is comparable to that of H(2) upon ionization. Removal of an electron from the Re-H or Re-D bonds leads to a quantum-mechanical inner sphere reorganization energy (lambda(QM)) of 0.34(1) eV. These observations suggest that even in these low symmetry molecules the orbital corresponding to the Re-H sigma bond and the Re-H vibrational mode is very localized. Theoretical calculations of the electronic structure and normal vibrational modes of CpRe(NO)(CO)H support a localized two-electron valence bond description of the Re-H interaction.