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.     

Spectroscopy and photophysics of binuclear ruthenium(II) complexes with nitrogen-containing heterocyclic bridging ligands

The absorption spectra at room temperature and the spectra, the quantum yields, and the decay times of the luminescence at 77 K of binuclear complexes [X(bpy)₂Ru(BL)Ru(bpy)₂Cl]²⁺ (bpy = 2,2′-bipyridyl; X = Cl, BL = pyrazine, 4,4′-bipyridyl, trans-1,2-bis(4-pyridyl)ethylene, and trans-1,2-bis(4-pyridyl)ethane and X = NO₂, BL = 4,4′-bipyridyl) in alcoholic (4: 1 EtOH-MeOH) solutions are studied. It is shown that the interaction between the metal centers (MCs) of the complexes affects the characteristics of the electronically excited states (EESs) of each of them and facilitates increasing the transition dipole moment Ru(d_π)→BL(π_*). The deactivation rate constants of the lowest electronically excited metal-to-ligand charge transfer (³MLCT) state of the complexes are determined. In an asymmetric binuclear complex, the energy transfer from MC(NO₂) to MC(Cl) is revealed, with the rate constant of this transfer being not smaller than 3.2 × 10¹⁰ s^?1.     

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.     

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.     

Specific solvent effects of hydroxylic solvents on the emission properties of ruthenium(ii)tris(2,2′-bipyridyl) chloride

The excited state of Ru(II)[bpy]₃ ²⁺ dissolved in hydroxylic solvents is subject to specific solvent effects, which were hitherto not understood on a quantitative basis. We determined the solvent effects of linear monovalent alcohols on the energy gap law of internal conversion with the help of lifetime and intensity measurements. An on-line method for measurement of the temperature dependence of quantum efficiencies was introduced. A modified Franck-Condon analysis of emission spectra by taking into account the shape of a Morse potential of the involved states was applied to compute excited-state energies.Abbreviations used Ru(II)[bpy]₃ ²⁺ ruthenium(II)tris(2,2-bipyridyl) chloride - MLCT metal-to-ligand charge transfer - PMT photomultiplier tube     

Orange Fluorescent Ru(III) Complexes Based on 4′-Aryl Substituted 2,2′:6′,2″-Terpyridine for OLEDs Application

A series of ruthenium (III) complexes of the formulae [Ru(4-Mephtpy)₂]Cl₃(1) [Ru(L ₁ )], [Ru(3,4,5-tmphtpy)₂]Cl₃(2) [Ru(L ₂ )], and [Ru(4-thptpy)₂]Cl₃(3) [Ru(L ₃ )], (where L?=?terpy?=?2.2′:6′2″ terpyridine ligands) are synthesized. The complexes were characterized by elemental analyses, spectroscopic and electrochemical data. The density functional theory (DFT) outlines the geometric optimisation and electronic charge transition of these complexes. Photophysical studies describe that the luminescence of Ru(III) complexes is due to electronic transition between the energy levels of singly unoccupied molecular orbitals (SUMO) and singly occupied molecular orbitals (SOMO). It also exhibits the potential charge transfer to π–π* and n–π* states due to MLCT and ILCT processes of the complexes. The observed bands centered at 591 and 620 nm demonstrate that these emissions originated from the transition of SUMO to SOMO energy levels, that is, from the radiative decay from the doublet exciton. Due to the heavy metal effect of Ru(III) ions the photophysical behaviour depends on the MLCT process. In conclusion, that the all three Ru(L ₁ -L ₃ ) complexes are fallen orange emission.     

The lowest metal-to-bipyridine charge-transfer excited state of [Cr(2,2′-bipyridine)(CO)4]

The DV-Xα molecular-orbital calculations have been carried out on [Crbpy(CO)₄](bpy,2,2′-bipyridine) and its electron attachment and detachment products. The one-electron attachment of [Crbpy(CO)₄] yields a complex of bipyridine anion radical, while the one-electron detachment results in ionization of the central metal atom. The lowest excited state of [Crbpy(CO)₄] is the metal-to-ligand charge-transfer (MLCT) excited state which consists of the bipyridine anion radical and the central metal ionized. The transition-state calculation predicts the lowest MLCT excited states at around 23～30×10³ cm^?1 and the lowest bipyridine (π,π^*) excitations at 36×10³ cm^?1 and 42～45×10³ cm^?1. The calculation also concludes that the MLCT excitation induces a counter migration of the other electrons not directly involved in the charge-transfer excitation. The configuration-interaction calculations predict the lowest MLCT excited singlet states at around 21～35×10³ cm^?1 and the lowest bipyridine (π, π^*) excited singlet states at 42～62×10³ cm^?1, while the emissive lowest MLCT triplet state is at 17×10³ cm^?1. The transition moments evaluated with the transition-state wavefunctions can reproduce qualitatively the observed absorption spectral profile. The intensity of the MLCT transitions is obtained from the allowed (π, π^*) transitions of coordinated bipyridine but is not due to the intrinsic transition moments of MLCT excitations.     

Ru L2,3 XANES theoretical simulation with DFT: A test of the core-hole treatment

Density functional theory (DFT)-based relativistic calculations were performed to model the Ru L-edge X-ray absorption near edge structure (XANES) spectra of the hexaammineruthenium complex [Ru(NH₃)₆]³⁺ and “blue dimer” water oxidation catalyst, cis,cis- [(bpy)₂(H₂O)Ru^IIIORu^III(OH₂)(bpy)₂]⁴⁺ (bpy is 2,2-bipyridine). Two computational approaches were compared: simulations without the core-hole and by modeling of the core-hole within the Z+1 approximation. Good agreement between calculated and experimental XANES spectra is achieved without including the core-hole. Simulations with algorithms beyond the Z+1 approximation were only possible in a framework of the scalar relativistic treatment. Time-dependent DFT (TD-DFT) was used to compute the Ru L-edge spectrum for [Ru(NH₃)₆]³⁺ model compound. Three different core-hole treatments were compared in a real-space full multiple scattering XANES modeling within the Green function formalism (implemented in the FEFF9.5 package) for the [Ru(Mebimpy)(bpm)(H₂O)]²⁺ complex. The latter approaches worked well in cases where spin–orbit treatment of relativistic effects is not required.     

Characterization of Ir(ppy)3 and [Ir(ppy)2 bpy]+ by infrared,Raman spectra and surface‐enhanced Raman scattering

The Raman and infrared spectra of fac ‐tris(2‐phenylpyridinato‐N,C2′)iridium(III), Ir(ppy)₃ and surface‐enhanced resonance Raman spectra of bis(2‐phenyl pyridinato‐) (2,2′bipyridine) iridium (III), [Ir(ppy)₂ (bpy)]⁺ cation were recorded in the wavenumber range 150–1700 cm⁻¹, and complete vibrational analyses of Ir(ppy)₃ and [Ir(ppy)₂ (bpy)]⁺ were performed. Most of the vibrational wavenumbers were calculated with density‐functional theory agree with experimental data. On the basis of the results of calculation and comparison of the spectra of both complexes and their analogue [Ru(bpy)₃]²⁺, we assign the vibrational wavenumbers for metal–ligand modes; metal–ligand stretching wavenumbers are 277/307 and 261/236 cm⁻¹ for Ir(ppy)₃, and 311/324, 257/270, 199/245 cm⁻¹ for [Ir(ppy)₂ bpy]⁺. Surface‐enhanced Raman scattering spectra of [Ir(ppy)₂ bpy]²⁺ were measured at two wavelengths on the red and blue edges of the low‐energy metal‐to‐ligand charge‐transfer band. According to the enhanced Raman intensities for the vibrational modes of both ligands ppy and bpy, the unresolved charge‐transfer band is deduced to consist of charge‐transfer transitions from the triplet metal to both ligands ppy and bpy. Copyright © 2010 John Wiley & Sons, Ltd.     

Optical and electrochemical characteristics of Ir(III) complexes with metalated 4-(4-bromophenyl)-2-methyl-1,3-thiazole and isocyanide,ethylenediamine, and diethyldithiocarbamate ligands

The influence of donor–acceptor properties of tert-butyl-, 2.6-dimethylphenyl-, and 4-bromophenyl-isocyanides (BuNC, XylNC, BpNC), ethylenediamine (En), and diethyldithiocarbamate ions (Dtc–) on the ¹H and ¹³C NMR, IR, optical, and electrochemical characteristics of Ir(III) complexes with metalated 4-(4-bromophenyl)-2-methyl-1,3-thiazole is studied. Enhancement of the donor properties of BpNC, XylNC, BuNC, En, and Dtc^– ligands leads to a bathochromic shift of metal-to-ligand charge transfer (MLCT) bands and to a decrease in the difference between the one-electron oxidation and reduction potentials of complexes. The bathochromic shift of the low-temperature phosphorescence of complexes in frozen (77 K) solutions with increasing donor properties of BpNC, XylNC, BuNC, En, and Dtc–ligands is caused by a decrease in the admixture of MLCT to the intraligand excited state of {Ir(bptz)₂}. Quenching of the phosphorescence of complexes in liquid solutions is attributed to the thermally-induced population of excited d–d* states with subsequent nonradiative deactivation.     

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.     

Sensitized Near-Infrared Luminescence From NdIII, YbIII and ErIII Complexes by Energy-Transfer From Ruthenium 1,3-Bis([1,10]Phenanthroline-[5,6-d]-Imidazol-2 -yl)Benzene

The luminescent ruthenium 1,3 -bis([1,10]phenanthroline-[5,6 -d]- imidazol-2 -yl)benzene (bpibH₂) complex, a potentially useful bridging ligand with a vacant diimine site, has been used as ‘metallo ligand’ to make heterodinuclear d–f complexes by attachment of a {Ln(dik)₃} fragment (dik?=?1,3-diketonate) at the vacant site. When Ln?=?Nd, Yb, or Er the lanthanide centre has low-energy f–f excited states capable of accepting energy from the ³MLCT excited state of the Ru(II) centre, there is quenching in the ³MLCT luminescence of the Ru(II) centre, that affords sensitized lanthanide(III) based luminescence in the near-IR region. Nd(III) was found to be the most effective at quenching the ³MLCT luminescence of the ruthenium component because of the high density of f–f excited states of the appropriate energy which make it as effective energy-acceptor compared to Er and Yb complexes.     

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.     

Theoretical study of Ir(III) complexes with cyclometalated alkenylquinoline ligands

Recently, it was reported that cyclometalated iridium(III) complexes of 2-((E)-2-phenyl-1-ethenyl)quinoline (PEQ) and 1-((E)-2-phenyl-1-ethenyl)isoquinoline (PEIQ) emitted saturated red light with high quantum efficiency and brightness. However, the energy difference between specific wavelengths due to the metal-to-ligand charge transfer (³MLCT) absorption and emission spectra showed rather large Stokes shifts, which originated at the predominant ³(π–π¹) ligand-based emission. In this paper, it is shown that these complexes are consistent with predominant ³(π–π¹) ligand-based emission. To develop the predominant ³MLCT emission of Ir complexes for a highly efficient phosphorescent complex suitable for red OLED devices, proper ligands having a highest occupied molecular orbital (HOMO) energy level similar to that of 2-phenylpyridine (ppy) ligand were designed to lead to strong mixing between π-orbitals of ligands and the 5d orbital of the centric iridium atom. In order to decrease the HOMO energy level and the lowest an occupied molecular orbital (LUMO) level simultaneously to maintain the same HOMO–LUMO energy gap, an electron accepting group such as F or CF₃ was introduced. By such manipulation of ligands in Ir complexes, it was theoretically possible to change the origin of emission in Ir complex from the predominant ligand-centered ³(π–π¹) excited state to the predominant ³MLCT excited state.     

DasL/K- und dasM/L-Einfangverhältnis von65Zink

We have investigated theL/K- and theL/M-capture ratio of⁶⁵Zn. For the transitions to the first excited state of⁶⁵Cu we obtained (N _L/N _K) _A =0.120±3% and (N _M/N _L) _A =0.153±13% and for both transitions to the groundstate and the first excited state simultaneously we found (N _L/N _K) _G =0.118±3%. The values for (N _L/N _K) agree well with the results of Santos Ocampo and Conway but are higher than the results of Totzek and Hoffmann. All values are discussed in view of the different theoretical values obtainable.     

Mössbauer and magnetic studies on the spin states of mono- and binuclear iron(III) complexes with quinquedentate ligand methyl-substituted pyridine and bridged by pyrazine or bis(pyridine) compounds

Mono- and binuclear iron(III) complexes with the general formula [FeXL] and [LFe-Y-FeL](BPh₄)₂ have been prepared and their spin states of the iron atom in the complexes has been investigated by means of the temperature-dependent Mössbauer spectroscopy and magnetic measurements, where X is a methyl-substituted pyridine, L denotes a quinquedentate Schiff-base derived from salicylaldehyde with N-(2-aminoethyl)-1,3-propanediamine and Y denotes bridged ligands such as pyrazine(pyr), 4,4′-pyridine(bpy), 4,4′-vinylenepyridine(vipy). On the basis of the Mössbauer and magnetic data, it was concluded that the spintransition characteristics depends on the methyl substituent of pyridine and the bridged ligand.     

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.     

Luminescence of charge transfer sensitizers anchored to metal oxide nanoparticles

The photoluminescence (PL) properties of inorganic charge transfer sensitizers anchored to nanometer sized metal oxide particles are presented. The charge transfer sensitizers are inorganic coordination compounds such as ruthenium tribipyridine, Ru(bpy)²⁺₃, which have long lived metal-to-ligand charge transfer (MLCT) excited states. The metal oxides are insulators or semiconductor materials in the form of powders, colloidal solutions, and porous nanocrystalline films. Time resolved PL decays from this and related sensitizers anchored to metal oxide surfaces are highly non-exponential. The MLCT excited states are quenched on semiconducting metal oxide particles by an apparent electron transfer mechanism. With some assumptions electron transfer rates from the MLCT excited states to the nanostructured surface are calculated. The PL properties of sensitizers bound to porous nanocrystalline TiO₂ films can be controlled electrochemically.     

Excitation and nonlinear saturation of stimulated backscatter in a bounded dissipative plasma

Nonlinear spatial theory of the backscatter decay interaction predicts that the reflectivity, under conditions of absolute instability and zero noise, cannot exceed 1 ? L₀²/4L_a², where L₀ is the basic gain length and L_a the absorption length of the excited electrostatic wave.