Spectroscopy and photophysics of chloro-bis-bipyridyl complexes of ruthenium(II) with pyridine ligands

The absorption, luminescence, and luminescence excitation spectra of ruthenium(II) complexes cis-[Ru(bpy)₂(L)Cl]⁺[bpy=2,2′-bipyridyl; L=NH₃, pyrazine, pyridine, 4-aminopyridine, 4-picoline, isonicotinamide, 4-cyanopyridine, 4,4′-bipyridyl, or trans-1,2-bis(4-pyridyl)ethylene] in alcoholic (4: 1 EtOH-MeOH) solutions are studied. At 77 K, the quantum yields and decay times of the luminescence of the complexes are measured and the deactivation rate constants of the lowest electronically excited metal-to-ligand charge transfer state (³MLCT) are determined. The linear correlation between the energy of the lowest state ³MLCT d _π(Ru)>π*(bpy) of the cis-[Ru(bpy)₂(L)Cl]⁺ complexes and the parameter pK_a of the free 4-substituted pyridines and pyrazine used as ligands is established.     

Spectroscopy and quantum-chemical calculations of nitro-bis-bipyridyl complexes of ruthenium(II) with 4-substituted pyridine ligands

The luminescence, absorption, and luminescence excitation spectra of complexes cis-[Ru(bpy)₂(L)(NO₂)]⁺ [bpy = 2,2′-bipyridyl, L = pyridine, 4-aminopyridine, 4-dimethylaminopyridine, 4-picoline, isonicotinamide, or 4,4′-bipyridyl] in alcoholic (4 : 1 EtOH–MeOH) solutions are studied at 77 K. A linear correlation is established between the energy of the lowest electronically excited metal-toligand charge transfer state d_π(Ru) → π*(bpy) of the complexes and the pK_a parameter of the free 4-substituted pyridines used as ligands L. The B3LYP/[6-31G(d)+LanL2DZ(Ru)] hybrid density functional method is used to optimize the geometry of complexes and calculate their electronic structure and the charge distribution on the atoms of the nearest environment of ruthenium(II) ions. It is shown that there exists a mutually unambiguous correspondence between the charge on the nitrogen atom of ligands L coordinated in the complex and the pK_a parameter of ligands. The calculated energies of the electronically excited metal-to-ligand charge transfer states of complexes linearly (correlation coefficient 0.99) depend on the charge on the nitrogen atom of ligands L, which completely agrees with the experimental data.     

Spectroscopic and quantum-chemical investigations of chloro-bis-bipyridyl complexes of ruthenium(II) with 4-substituted pyridine ligands

The luminescence spectra of cis-[Ru(bpy)₂(L)Cl]⁺ (bpy is 2,2′-bipyridyl; L is pyrazine, pyridine, 4-amino-pyridine, 4-picolin, isonicotinamide, 4-cyanopyridine, or 4,4′bipyridyl) complexes are studied in alcoholic (4: 1 EtOH-MeOH) solutions at 77 K. A linear correlation is found between the energy of the lowest electronically excited metal-to-ligand charge transfer (³MLCT) state d _π(Ru) → π* (bpy) and the parameter pK _a of the free 4-substituted pyridines and pyrazine used as ligands L. The [B3LYP/6-31G + LanL2DZ(Ru)] hybrid method of the density functional theory is used to optimize the geometry of complexes and calculate their electronic structure and the charge distribution on the atoms of the nearest environment of the ruthenium ion. It is shown that there exists a linear unambiguous correlation between the negative charge on the nitrogen atom (qN ^L) of ligands L coordinated in the complex and the parameters pK _a of free ligands. The calculated energies of ³MLCT excited states almost linearly (correlation coefficient 0.958) depend on the charge qN ^L, which completely agrees with experimental data.     

Photophysics of bis-bipyridyl complexes of ruthenium(II) with triphenylphosphine

We studied the spectral-luminescent characteristics of the luminescence of mixed-ligand polypyridine-phosphine complexes of ruthenium(II) cis-[Ru(bpy)₂(PPh₃)X](BF₄) _n with ligands 2,2′-bipyridyl (bpy) and triphenylphosphine (PPh₃) and X = Cl⁻, Br⁻, CN⁻, NO₂⁻, NH₃, MeCN, pyridine (py), 4-aminopyridine (pyNH₂), and 4,4′-bipyridyl (4,4′-bpy) in a 4: 1 EtOH-MeOH alcoholic mixture at 77 K. The radiative and nonradiative deactivation rate constants of the lowest electronically excited state of the complexes are determined. We find that triphenylphosphine has a greater effect on the photophysical characteristics of ruthenium(II) complexes compared to π-acceptor strong-field ligands, such as MeCN, CN⁻, and NO₂⁻. At the same time, the characteristics of complexes cis-[Ru(bpy)₂(PPh₃)X] ⁿ⁺ considerably depend on the nature of the second monodentate ligand X, which is coordinated to ruthenium(II), and correlate with its position in the spectrochemical series of ligands.     

The key Cl− ligand for metal‐to‐ligand charge transfer in mononuclear terpyridine ruthenium(II) and binuclear ruthenium(II) tetrapyridylpyrazine complexes

Electronic structures of binuclear ruthenium complexes [Ru₂(terpy)₂(tppz)]⁴⁺ ( 1A ) and [Ru₂Cl₂(L)₂(tppz)]²⁺ {L = bpy ( 2A ), phen ( 3A ), and dpphen ( 4A )} were studied by density functional theory calculations. Abbreviations of the ligands (Ls) are bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, dpphen = 4,7‐diphenyl‐1,10‐phenanthroline, terpy = 2,2′:6′,2″‐terpyridine, and tppz = tetrakis(2‐pyridyl)pyrazine. Their mononuclear reference complexes [Ru(terpy)₂]²⁺ ( 1B ) and [RuClL(terpy)]⁺ {L = bpy ( 2B ), phen ( 3B ), and dpphen ( 4B )} were also examined. Geometries of these mononuclear and binuclear Ru(II) complexes were fully optimized. Their geometric parameters are in good agreement with the experimental data. The binuclear complexes were characterized by electrospray ionization mass spectrometry, UV–Vis spectroscopy, and cyclic voltammograms. Hexafluorophosphate salts of binuclear ruthenium complexes of 3A and 4A were newly prepared. The crystal structure of binuclear complex 1A (PF₆)₄ was also determined. Orbital interactions were analyzed to characterize the metal‐to‐ligand charge‐transfer (MLCT) states in these complexes. The Cl^? ligand works to raise the orbital energy of the metal lone pair, which leads to the low MLCT state. Copyright © 2011 John Wiley & Sons, Ltd.     

High-efficiency Red Electrofluorescence Devices Employing a Rhenium Complex as Phosphorescent Sensitizer

Efficiencies of up to 7.81 cd/A and brightness of 8843 cd/m² are obtained based on green–yellow phosphorescent material, fac 4, 4′-bi (tert-butyl)-2, 2′-bipyridine Re(CO)₃Cl[(Bu ^t bpy)Re(CO)₃Cl] doped into 4,4′-N,N′-dicarbazole-biphenyl (CBP) host. We also fabricate high-efficiency red devices by introduction of (Bu^tbpy)Re(CO)₃Cl as a sensitizer, and the undoped ultrathin layer 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as fluorescent acceptor. Förster energy of triplet and singlet are efficient due to appropriate overlap between emission spectrum of (Bu ^t bpy)Re(CO)₃Cl and absorption spectrum of DCJTB.     

DFT study of electronic structure and optical properties of some Ru- and Rh-based complexes for dye-sensitized solar cells

The paper reports Time Dependent Density Functional Theory (TD DFT) calculations providing the structure, electronic properties and spectra of [Ru(II)(bpy)_{3? n} (dcbpy) _n ]²⁺ and [Rh(III)(bpy)_{3? n} (dcbpy) _n ]³⁺ complexes, where bpy?=?2,2′-bipyridyl, dcbpy?=?4,4′-dicarboxy-2,2′-bipyridyl, and n?=?0,?1,?2,?3, studied as possible pigments for dye-sensitized solar cells. The role of the metallic ion and of the COOH groups on the optical properties of these complexes are compared and contrasted and their relevance as dyes for hybrid organic–inorganic photovoltaic cells is discussed. It was found that the optical spectra are strongly influenced by the metallic ion, with visible absorption bands for the Ru(II) complexes and only ultraviolet bands for the Rh(III) complexes. Upon excitation, the extra positive charge of the Rh³⁺ centre tends to draw electrons towards the metal ion, facilitating some charge transfer from the ligand to the metal, whereas in the case of the Ru²⁺ ion the electron transfer is clearly from the metal to the ligand. The carboxyl groups play an important role in strengthening the absorption bands in solution in the visible region. Of the complexes studied, the most suited as pigments for dye-sensitized solar cells are the [Ru(II)(bpy)_{3? n} (dcbpy) _n ]²⁺ complexes with n?=?1 and 2. This is based on the following arguments: (i) their intense absorption band in the visible region, (ii) the presence of the anchoring groups allowing the bonding to the TiO₂ substrate and the charge transfer, and (iii) the good energy level alignment with the conduction band edge of the semiconducting substrate and the redox level of the electrolyte.     

Synthesis and spectroscopic and electrochemical properties of binuclear complexes of Au(III) bridged by 6,7-dimethyl-2,3-di(2-pyridyl) quinoxaline

A method of synthesis of new diimine complexes of Au(III) with a four-dentate bridging ligand 6,7-dimethyl-2,3-di(2-pyridyl) quinoxaline (Ddpq), [Au₂(μ-Ddpq)Cl₄]Cl₂ and [(AuN^N)₂(μ-Ddpq)](NO₃)₆, where N^N is ethylenediamine, 2,2′-bipyridyl, or 1,10-phenanthroline, is described and the composition, structure, and properties of these complexes are studied. The coordination-induced chemical shifts in the ¹H NMR spectra are determined, as well as the spectral-luminescent and electrochemical parameters of the complexes. The nature of the energetically lowest spin-allowed ¹(π-d*)-and spin-forbidden ³(π-π*) states is established.     

Photophysics of the adsorbed bipyridyl complexes of ruthenium(II) with phosphines

Luminescence of the ruthenium(II) complexes cis-Ru(bpy)₂(CN)₂ (I), cis-[Ru(bpy)₂(PPh₃)CN](BF₄) (II), and cis-Ru(bpy)(dppe)(CN)₂ (III)[bpy=2.2′-bipyridyl, PPh₃=triphenylphosphine, dppe=1,2-bis(diphenylphosphino)ethane], adsorbed on silicon oxide (Aerosil) were studied at a temperature of 77 K. The luminescence spectra, decay times, and quantum yields were measured, and the intermolecular rate constants of radiative transitions and nonradiative decay of the excited electronic state with the metal-to-ligand charge transfer (MLCT) were determined. It is found that the adsorption of the complex is accompanied by a decrease in the energy of the radiative MLCT state and by a considerable acceleration of its nonradiative decay. It is concluded that the interaction of the complexes with the surface adsorption centers occurs via formation of a strong hydrogen bond with a hydroxyl-hydrate cover, the interaction of complexes in the ³MLCT state being stronger than in the ground state. The additive (in the number of phosphorus atoms coordinated to the central ruthenium ion), a shift of the absorption and luminescence bands to shorter wavelengths in the sequence of complexes I–III, is retained when the complexes transform from solutions to the absorbed state.     

Synthesis,Characterization and Luminescence Sensitivity with Variance in pH,DNA and BSA Binding Studies of Ru(II) Polypyridyl Complexes

Three ruthenium(II) polypyridyl complexes, [Ru(phen)₂(mip)](ClO₄)₂ (1) (phen =1,10-Phenanthroline), [Ru(bpy)₂(mip)](ClO₄)₂ (2) (bpy = 2,2’bipyridyl) and [Ru(dmb)₂(mip)](ClO₄)₂ (3) (dmb = 4, 4′-dimethyl 2, 2′-bipyridine), were synthesized with an intercalative ligand mip (2-morpholino-1H-imidazo[4,5-f][1, 10]phenanthroline) and characterized by ¹H, ¹³C–NMR, IR, UV-vis, mass spectra and elemental analysis. pH effect, ion selectivity (cations, anions) and solvent sensitivity of complexes were studied. The interaction of these complexes with DNA was performed using absorption, emission spectroscopy and viscosity measurements. The experimental results indicated that the two complexes interacted with calf thymus DNA (CT-DNA) by intercalative mode. BSA (Bovine Serum Albumin) protein binding of these complexes was studied by UV-visible and fluorescence techniques. The binding capacity of these complexes was explained theoretically by molecular docking method.     

Electrogenerated chemiluminescence quenching of Ru(bpy)3 2+ (bpy=2,2′-bipyridine) in the presence of acetaminophen,salicylic acid and their metabolites

Quenching of Ru(bpy) ₃²⁺ (bpy=2,2′-bipyridine) coreactant electrogenerated chemiluminescence (ECL) has been observed in the presence of acetaminophen, salicylic acid and related complexes. However, no quenching is observed with the acetylsalicylic acid. In most instances, quenching is observed with 100-fold excess of quencher (compared to ECL luminophore) with complete quenching observed between 10,000 and 100,000 fold excess. Fluorescence and UV–vis experiments coupled with bulk electrolysis support the formation of benzoquinone products upon electrochemical oxidation. The mechanism of quenching may involve the interaction of the electrochemically generated benzoquinone species with (i) the ^?Ru(bpy)₃²⁺ excited state or (ii) highly energetic coreactant radicals.     

New luminescing complexes of Pd(II) with 2-(phenyl)benzothiazolate

The luminescent properties of the complexes [PdBt(μ-Cl)]₂, [PdEnBt]ClO₄, and [PdBryBt]PF₆ (where Bt is 2-(phenyl)benzothiazolate-N,C²′-ion, En is 1,2-(diamine)ethane, and Bpy is 2,2′-bipyridyl) are studied and a qualitative diagram of their electronically excited states is presented.     

Synthesis, DNA-binding, Cytotoxicity, Photo Cleavage, Antimicrobial and Docking Studies of Ru(II) Polypyridyl Complexes

Three Ruthenium(II) polypyridine complexes, [Ru(phen)₂(mipc)]²⁺(1), [Ru(bpy)₂(mipc)]²⁺ (2) and [Ru(dmb)₂(mipc)]²⁺(3) [mipc?=?2-(6-methyl-3-(1H-imidazo[4, 5-f][1,10]-phenanthroline-2-yl)-4H-chromene-4-one, phen?=?1,10-phenanthroline,bpy?=?2, 2′bipyridine,dmb?=?4, 4′-dimethyl-2, 2′-bipyridine] have been synthesized and characterized by elemental analysis, IR, UV–Vis, ¹H& ¹³C NMR and mass spectra. The DNA-binding properties of the Ruthenium(II) complexes were investigated by spectrophotometric methods, viscosity measurements and light switch studies. These three complexes have been focused on photo activated cleavage studies with pBR-322 and antimicrobial studies. Experimental results indicate that the three complexes intercalate into DNA base pairs and follows the order of 1?>?2?>?3 respectively. Molecular docking studies also support the DNA interactions with complexes through hydrogen bonding and vander Waal’s interactions. Cytotoxicity studies with Hela cell lines has been revealing about anti tumor activity of these complexes.     

Comparative DFT study on the role of conformers in the ruthenium alkylidene‐catalyzed ROMP of norborn‐2‐ene

Comparative quantum chemical calculations on the reaction pathways for the formation of ruthena(IV)cyclobutanes from both 1^st‐ and 2^nd‐generation Grubbs catalysts of the general formula RuX₂(L)(L′)(?CH₂) (L = PCy₃ or 1,3‐dimesityl‐4,5‐dihydroimidazolin‐2‐ylidene, L′ = PCy₃) and norborn‐2‐ene (NBE) were carried out on the B3LYP/LACVP** level in dependence on the ligand X = I, Br, Cl, and F. The mechanism proposed by Straub for the formation of (one) active and (three) inactive NBE–Ru–carbene complexes for non‐cyclic alkenes was applied to the cyclic alkene NBE. In RuX₂(PCy₃)₂(?CH₂), the inactive NBE–Ru–carbene complex is energetically more stable than the active one; however, in RuX₂(IMesH₂)(PCy₃)(?CH₂), the active NBE–Ru–carbene complex is more stable than the inactive one. In due consequence, the possible rate limiting barrier for the conversion of the NBE–Ru–carbene complex into the corresponding metallocyclobutane (MCB) is systematically larger in the case of 1^st‐generation Grubbs catalysts than of 2^nd‐generation Grubbs catalysts due to an additional re‐arrangement for the formation of an active π‐complex from the more stable (inactive) conformer. This correlates with the observed reactivity of both types of initiators. There is a strong influence of the ligands L and X on the conformational properties and relative stabilities of the 14‐electron intermediates, which has a direct effect on the distribution of the inactive and active conformations of the corresponding Ru–carbene–NBE complexes. A direct correlation between the conformational properties of the 14‐electron intermediates and the relative stabilities of the active Ru–carbene–NBE complexes was observed. Copyright © 2008 John Wiley & Sons, Ltd.     

Syntheses,X‐ray crystal structures,and emission properties of protonated tripyridyltriazines and their ruthenium(II) complexes

A series of metal‐free compounds, ie, planar triprotonated triazine, triazineH₃Cl(PF₆)₂ ( 1 ), planar triprotonated triazineH₃Br(PF₆)₂ ( 2 ), and nonplanar monoprotonated triazineHPF₆ ( 3 ), were prepared. Abbreviations used are triazine = tri‐2‐pyridyltriazine. Ruthenium complexes [RuCl(bpy)(L)](PF₆), [RuCl(bpy)(L)](PF₆)₂, and [Ru(L)₂](PF₆)₂ were also prepared, where bpy is 2,2′‐bipyridine and L's are triazine ( 4 ) and monoprotonated triazine ( 5 ), respectively. Ruthenium complexes [Ru(triazine)₂](PF₆)₂ ( 6 ) were also prepared and crystallized. The X‐ray crystal structures of the 3 compounds 1 , 2 , and 3 and the complex 6 were determined. They were also characterized by electrospray ionization mass spectrometry, UV‐vis spectroscopy, and density functional theory calculations.     

Optical oxygen sensing materials based on trinuclear starburst ruthenium(II) complexes assembled in mesoporous silica

The preparation and oxygen sensing properties of optical materials based on two trinuclear starburst ruthenium(II) complexes: [Ru₃(bpy)₆(TMMB)]⁶⁺ (1) and [Ru₃(phen)₆(TMMB)]⁶⁺ (2) (bpy=2,2′-bpyridine, phen=1,10-phenathroline, TMMB=1,3,5-tris[2-(2′-pyridyl)benzimidazoyl]methylbenzene) assembled in two mesoporous silicate (MS) are described in this paper. The luminescence of Ru complexes/silicate assemble materials can be quenched by molecular oxygen with good sensitivity (I₀/I₁>5 for 2/MS and I₀/I₁>3 for 1/MS), indicating that trinuclear starburst Ru(II) complexes/MS systems are sensitive to oxygen molecules.     

The formation of the superheavy hydrogen isotope <Superscript>6</Superscript>H in the absorption of stopped π<Superscript>−</Superscript>-mesons by nuclei

An experimental search for the superheavy hydrogen isotope ⁶H was conducted through studying the absorption of stopped π^?-mesons by ⁹Be and ¹¹B nuclei. A structure in the missing mass spectrum caused by the resonance states of ⁶H was observed in three reaction channels, namely, ⁹Be(π^?, pd)X, ¹¹B(π^?, d³He)X, and ¹¹B(π^?, p⁴He)X. The parameters of the lowest state E_r=6.6±0.7 MeV and Γ=5.5±2.0 MeV (E_r is the resonance energy with respect to the disintegration into the triton and three neutrons) are evidence that ⁶H is a more weakly bound system than ⁴H and ⁵H. Three excited states of ⁶H were observed. Their resonance levels (E_1r=10.7±0.7 MeV, Γ_1r=4±2 MeV, E_2r=15.3±0.7 MeV, Γ _2r=3±2 MeV, and E_3r=21.3±0.4 MeV, Γ_3r=3.5±1.0 MeV) are energetically capable of disintegrating into six free nucleons.     

Signature splitting in two quasiparticle rotational bands of <Superscript>180,182</Superscript>Ta

The signature splittings in K^π = 1 ⁺: 7 /2[404] _π?9 /2[624] _ν, K^π = 0^?: 9 /2[514] _π?9 /2[624] _ν bands of ¹⁸⁰Ta and K^π = 0^?: 7 /2[404] _π?7 /2[503] _ν, K^π = 1^?: 5 /2[402] _π?3 /2[512] _ν, K^π = 1⁺: 7 /2[404] _π?9 /2[624] _ν bands of ¹⁸²Ta are analysed within the framework of two-quasiparticle rotor model. The phase as well as magnitude of the experimentally observed signature splitting in K^π = 1⁺ band of ¹⁸⁰Ta, which could not be explained in earlier calculations, is successfully reproduced. The conflict regarding placement of a 12 ⁺ level in K^π = 1 ⁺: 7 /2 ⁺[404] _π?9 /2 ⁺[624] _ν ground-state rotational band of ¹⁸⁰Ta is resolved and tentative nature of K^π = 0^?: 7 /2[404] _π?7 /2[503] _ν, K^π = 1⁺: 7 /2[404] _π?9 /2[624] _ν bands observed in ¹⁸²Ta is confirmed. As a future prediction for experimentalists, these two-quasiparticle structures observed in ¹⁸⁰Ta and ¹⁸²Ta are extended to higher spins.     

TOTAL ASSIGNMENT OF 1H AND 13C NMR SPECTRA OF A BRIDGED TRIRUTHENIUM CLUSTER-POLYPYRIDINE DIMER BASED ON 2D (COSY,HMQC, AND HMBC) TECHNIQUES

The bridged ruthenium cluster-polypyridine dimer [Ru₃O(CH₃COO)₆(py)₂(tmbpy)Ru(bpy)₂(Cl)](PF₆)₂ (py = pyridine, = 2, 2′-bipyridine and tmbpy = 4, 4′-trimethylenedipyridine) has been synthesized and structurally characterized based on ¹H and ¹³C NMR spectroscopy. This species exhibits a complex pattern of NMR signals due to the presence of a paramagnetic [Ru₃O] core and seven non-equivalent aromatic rings. 2D NMR (COSY, HMQC and HMBC) correlation techniques have been required for the total assignment of the ¹H and ¹³C NMR spectra.