A new strategy to build caged-compounds is presented. The approach based on heterolytic photocleavage of a metal−ligand bond in coordination compound. ruthenium polypyridine complex, containing the neurocompound 4-amino pyridine (4AP) used as core phototrigger. biomolecule released by irradiation with visible light (>480 nm). liberated 4AP promotes activation leech neuron means blocking its K+ channels. syntesis, characterization, and inherent advantages this method are discussed.

Octahedral Ru(II) polypyridyl complexes constitute a superb platform to devise photoactive triggers capable of delivering entire molecules in reliable, fast, efficient and clean way. Ruthenium coordination chemistry opens the way caging wide range molecules, such as amino acids, nucleotides, neurotransmitters, fluorescent probes genetic inducers. Contrary other phototriggers, these Ru-based caged compounds are active with visible light, can be photolysed even at 532 nm (green), enabling use...

The interaction of metal complexes with ionic liquids, a particular focus on the stability and surface concentration centers, is crucial in applications involving catalysts based supported liquids.

The splitting of dinitrogen (1 atm, THF, 25 °C) by Mo(N[R]Ar)3 (R = C(CD3)2CH3, Ar 3,5-C6H3Me2) giving 2 equiv nitride N⋮Mo(N[R]Ar)3 is found to be accelerated in the presence sodium amalgam. Careful control concentration led isolation and characterization anionic complex, [(THF)xNa][(N2)Mo(N[R]Ar)3], where x from 0 3. Via electrochemical experiments synthetic studies, [(THF)xNa][(N2)Mo(N[R]Ar)3] a key intermediate acceleration N2 Accordingly, an electron acceptor, reacts with give neutral...

Reaction of Mo(N[R]Ar)(3) (R = (t)Bu or C(CD(3))(2)CH(3)) with N(2)O gives rise exclusively to a 1:1 mixture nitride NMo(N[R]Ar)(3) and nitrosyl ONMo(N[R]Ar)(3), rather than the known oxo complex OMo(N[R]Ar)(3) dinitrogen. Solution calorimetry measurements were used determine heat reaction and, independently, NO. Derived from latter is an estimate (155.3 +/- 3.3 kcal.mol(-1)) molybdenum-nitrogen bond dissociation enthalpy for terminal nitrido complex, NMo(N[R]Ar)(3). Comparison new data...

The NIR and IR spectroscopic properties of the cyanide-bridged complex, trans-[Ru(dmap)4 {(μ-CN)Ru(py)4 Cl}2 ](3+) (py=pyridine, dmap=4-dimethylaminopyridine) provide strong evidence that this trimetallic ion behaves as a Class III mixed-valence species, first example reported system. This has been accomplished by tuning energy fragments in complex to compensate for intrinsic asymmetry cyanide bridge. Moreover, (TD)DFT calculations accurately predict spectra confirms its delocalized nature.

Abstract Controlling the local concentration of metal complexes at surface ionic liquids (ILs) is a highly sought‐after objective due to its pivotal implications in supported liquid phase (SILP) catalysis. Equally important avoid per‐ and polyfluorinated substances environmental concerns. Herein, we investigate enrichment Ru polypyridyl with fluorine‐free alkylic side groups varying lengths shapes, using hydrophilic IL [C 2 C 1 Im][OAc] as solvent. Additional charged carboxylate are included...

The g factor components of [(NC)5M(NO)]3- were calculated by relativistic density functional calculations, including spin−orbit coupling. values are in good agreement with previous (M = Fe) and new experimental results Ru, Os). Spin−orbit coupling effects particularly strong for the osmium system. Whereas MII−NO• is most appropriate formulation describing spin distribution, there substantial contribution (ca. 25%) from metal to singly occupied MO each case.

Neuroactive compounds can be photoreleased by means of two-photon excitation using a new kind transition metal-based caged compound.

The first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+). Although there experimental evidence extensive electronic coupling across μ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions weak to moderately coupled Ru(III) ions bridge. We present comprehensive investigation, combined calculations. experiments demonstrate both that strong in blue dimer its effects...

In this article, we report the structural, spectroscopic, and electrochemical properties of cyanide-bridged complex salts trans-[(NC)Ru(II)(L)4(μ-CN)Ru(II)(py)4Cl]PF6 trans-[Ru(II)(L)4{(μ-CN)Ru(II)(py)4Cl}2](PF6)2 (L = pyridine or 4-methoxypyridine). The mixed-valence forms these compounds show a variety metal-to-metal charge-transfer bands, including one arising from charge transfer between remote ruthenium units. latter is more intense when L 4-methoxypyridine points to role bridging unit...

The influence of the solvent on structure and IR spectrum [Fe(CN)(5)NO](2)(-) ion is investigated by using gradient corrected density functional theory. spectra are also measured different solvents results obtained compared with predicted ones. We have treated effects a continuum model, based Onsager's reaction field approach; in order to mimic strong specific interactions, calculations were performed complex protonated at cyanide trans nitrosyl group. predict only qualitatively most...

Clear spectroscopic signatures of ligand field states in the MLCT decay cascade of<italic>trans</italic>-[Ru(L)₄(NCS)₂] (L = pyridine or 4-methoxypyridine) were found. (TD)DFT calculations reveal presence both and LMCT transient absorption bands.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCrystal and Molecular Structure, Spectroscopic Properties, Electrophilic Reactivity of Sodium Pentacyanonitrosylosmate(II) DihydrateLuis M. Baraldo, Marcela S. Bessega, Graciela E. Rigotti, Jose A. OlabeCite this: Inorg. Chem. 1994, 33, 25, 5890–5896Publication Date (Print):December 1, 1994Publication History Published online1 May 2002Published inissue 1 December...

We report the synthesis, characterization, and spectroscopic properties of a family trinuclear cyano-bridged mixed-valent compounds, trans-[Ru(II)L(4)[NCFe(III)(CN)(5)](2)](4-), trans-[Ru(II)L(4)[CNFe(III)(CN)(5)](2)](4-), cis-[Ru(II)(bpy)(2)[NCFe(III)(CN)(5)](2)](4-) (L = pyridine, 4-tert-butylpyridine, 4-methoxypyridine). Tetraphenylphosphonium salts complexes trans-[Ru(II)L(4)[NCFe(III)(CN)(5)](2)](4-) pyridine 4-tert-butylpyridine) crystallize in space groups C2 P2(1)/c, respectively,...

The new complex trans-[NCRu(py)(4)(CN)Ru(py)(4)NO](PF(6))(3) (I) was synthesized. In acetonitrile solution, I shows an intense visible band (555 nm, epsilon = 5800 M(-1) cm(-1)) and other absorptions below 350 associated with d(pi) --> pi(py) transitions. is presently assigned as a donor-acceptor charge transfer (DACT) transition from the remote Ru(II) to delocalized [Ru(II)-NO(+)] moiety. Photoinduced release of NO observed upon irradiation at DACT band. Application Hush model reveals...

The [OsIII(CN)6]3- anion is prepared by chemical oxidation in aqueous solution and isolated as yellow prisms of [Ph4P]3[OsIII(CN)6]·6H2O (1). This species crystallizes the triclinic space group P1̄ with cell parameters a = 13.7609(11) Å, b 16.2275(13) c 17.0895(14) α 91.4040(10)°, β 109.3600(10)°, γ 102.3970(10)°, V 3497.4(5) Å3, Z 2. slightly distorted octahedral moiety displays Os−C C−N bond lengths that average 2.058 1.146 respectively. Spin−orbit-coupling splitting ground-state term...

We report the synthesis, structure and properties of cyanide-bridged dinuclear complex ions [Ru(L)(bpy)(μ-NC)M(CN)5]2−/− (L = tpy, 2,2′;6′,2′′-terpyridine, or tpm, tris(1-pyrazolyl)methane, bpy 2,2′-bipyridine, M Fe(II), Fe(III), Cr(III)) related monomers [Ru(L)(bpy)X]2+ (X CN− NCS−). All monomeric compounds are weak MLCT emitters (λ 650–715 nm, ϕ ≈ 10−4). In Fe(II) Cr(III) systems, cyanide bridge promotes efficient energy transfer between Ru-centered state a Fe(II)- Cr(III)-centered d–d...

We report here the spectroscopic properties of four very closely related mixed-valence cyanide-bridged bimetallic complexes, trans-[Ru(T)(bpy)(μ-NC)Ru(L)4(CN)]3+ (T = tris(1-pyrazolyl)methane (tpm, a) or 2,2′;6′,2″-terpyridine, (tpy, b), and L pyridine (py, 1) 4-methoxypyridine (MeOpy, 2)). In acetonitrile all complexes present intervalence charge transfer (IVCT) transitions in NIR region, but their intensities are widely different, with intensity transition observed for 1a–b3+ around times...

Abstract The NIR and IR spectroscopic properties of the cyanide‐bridged complex, tran s‐[Ru(dmap) 4 {(μ‐CN)Ru(py) Cl} 2 ] 3+ (py=pyridine, dmap=4‐dimethylaminopyridine) provide strong evidence that this trimetallic ion behaves as a Class III mixed‐valence species, first example reported system. This has been accomplished by tuning energy fragments in complex to compensate for intrinsic asymmetry cyanide bridge. Moreover, (TD)DFT calculations accurately predict spectra confirms its delocalized nature.

Upon MLCT photoexcitation, {(tpy)Ru} becomes the electron acceptor in mixed valence {(tpy˙⁻)Ru^III−δ-NC-M^II+δ} moiety, reversing its role as donor ground-state analogue.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTComparative Bonding and Photophysical Properties of 2,2'-Bipyridine 2,2'-Bipyrazine in Tetracyano Complexes Containing Ruthenium OsmiumMonica E. Garcia Posse, Nestor Katz, Luis M. Baraldo, Diego D. Polonuer, Claudio G. Colombano, Jose A. OlabeCite this: Inorg. Chem. 1995, 34, 7, 1830–1835Publication Date (Print):March 1, 1995Publication History Published online1 May 2002Published inissue 1 March...