Photophysics of mixed ligand complexes of ruthenium(II) with 2,2′-bipyridyl and phosphines

Luminescence of mixed ligand complexes of ruthenium(II) of the types cis-Ru(bpy)₂X₂(I), cis-[Ru(bpy)₂(PPh₃)X](BF₄)(II), and cis-Ru(bpy)(PP)X₂(III) (X = CN, NO₂, PPh₃ is triphenyl phosphine; PP is 1,2-bis(diphenylphospino)ethane (dppe) and cis-,2-bis(diphenylphosphino)ethylene (dppene)) is studied in alcohol matrices (EtOH/MeOH, 4:1) frozen at 77 K. A sequence of complexes I–III exhibits an additive (in the number of phosphorous atoms) blue shift of the absorption and luminescence bands and an increase in the quantum yield of luminescence and in the excited-state lifetime. The rate constant of nonradiative deactivation of the excited state decreases more than by an order of magnitude in the sequence I–III of cyano complexes and only by three times in a sequence of nitro complexes. This is assumed to be caused by a specific (in the hydrogen bond type) interaction of nitro groups of complexes with a proton solvent.     

Viscosity and Temperature Effects on the Rate of Oxygen Quenching of Tris-(2,2′-bipyridine)ruthenium(II)

We compare the bimolecular quenching rate constant (k₂) of luminescent tris(2,2′-bipyridine)ruthenium(II) by oxygen in water, ethylene glycol and glycerol as a function of temperature and viscosity to several theoretical models. The Smoluchowski equation with experimentally determined diffusion coefficients produced calculated values that were in the best agreement with experiment. For the less viscous solvent, water, this equation produced a value that was approximately an order of magnitude larger than the experimental value. With an increase in solvent viscosity, the Smoluchowski value approached the experimental value. Using the Smoluchowski equation with calculated diffusion coefficients based on the known radii of the reacting species produced deviations an order of magnitude larger in water and a factor of two or three lower in ethylene glycol and glycerol. If an assumption is made that the radii of both molecules are equal, we have the Stokes Einstein equation, and the only parameters become temperature and viscosity. Using this relationship, the calculated values for water are about a factor of two larger and with ethylene glycol and glycerol about a factor of 6 smaller than experimental data. These results show that bimolecular quenching is a more complex process affected by many parameters such as solvent cage effects in addition to viscosity and temperature.     

Magnetic-field and temperature effects on the optical properties of dicyano-2,2′-bipyridyl-platinum(II) single crystals

Studies of the polarized emission of [Pt(CN)₂(bipy)] single crystals as function of temperature (1.9 K ⩽ T ⩽ 295 K) and homogeneous magnetic fields (0 ⩽ H ⩽ 6 T), and the temperature dependence of the polarized absorption spectrum are reported. Raising the temperature from 1.9 to 7 K or increasing the magnetic field from 0 to 1 T results in a blue shift of ≈175 cm^-1 in the E ⊥ a polarized emission (E: electric field vector, a: crystallographic a axis). Between 1.9 and 295 K at H = 0) and between 0 and 6 T (at T = 1.9 K), the emission lifetime decreases by factors of ≈10³ and ≈10², respectively. The results are explained within the C'_2v symmetry of the single complex assuming a coupling between neighboring central ions.     

Spectroscopic Properties and Electronic Structure of (L-Glutamato)(2, 2′-Bipyridine) copper(II)

Cu(L-glu)(bpy)(L-glu = L-glutamato; bpy = 2, 2′-bipyridine) was prepared. Its electronic absorption spectrum and photoacoustic spectrum were recorded at room temperature. They were compared with each other and compared quantitatively with ligand field theory(LFT) and the radical wave function of non-free ions^[1–3]. Therefore, the electronic structure was also investigated with its spectrum behaviors and PLFT^[1–3].     

Effect of the donor–acceptor properties of ligands on the spectroscopic and electrochemical properties of mixed-ligand complexes of Pt(II) and Ir(III) with cyclometalated 2-phenylbenzothiazole

The results of the spectroscopic NMR (¹H, ¹³C, and ¹⁹⁵Pt), infrared, optical, and voltammetric characteristics of the mixed-ligand complexes of Pt(II) and Ir(III) with metalated 2-phenylbenzothiazole and tert-butylisocyanide (tBuNC), acetonitrile (AN), ethylenediamine (En), O-ethyldithiocarbamate (Exn^–), and diethyldithiocarbamate (Dtc–) ions are presented. It is demonstrated that the change in donor–acceptor interaction of ligands tBuNC, AN, En, Exn^–, and Dtc^– with metal leads to an increase in the energy of the highest occupied molecular orbital of the complexes and is accompanied by a shift of the cathode potential of the metal-centered oxidation, a bathochromic shift of the spin-allowed and spin-forbidden metal-tocyclometalated ligand optical charge transfer transitions, and an increase the degree of mixing of the ¹MLCT and triplet intraligand states, responsible for the phosphorescence of the complexes.     

Theoretical studies on the geometrical and electronic structures of supramolecule bis(2,2′-bipyridine)-5-amino-1,10-phenanthroline ruthenium(II)/functionalized SWCNT dyads

Functionalization of carbon nanotube (CNT) with multiple redox and photo active entities is one of the extensive processes due to its importance in building molecular or supramolecular electronic devices, solar energy storage and conversion systems. Thus, to have better understanding about structural aspects and correct electronic structure of these large systems, the quantum studies have gained increased popularity. In present study, we have investigated the structural and electronic properties of functionalized CNTs (fCNTs) with [Ru(bpy)₂(5-NH₂-1,10-phen)]⁺², (Ru-bpy-phen)⁺², supramolecule based on DFT calculations. Main attention has been applied to obtain stable configuration, binding energies and effect of functionalization on electronic behavior of the selected supramolcule. We also evaluate the effect of nanotube’s diameter and chirality on electronic properties of considered supramolecule. Calculated binding energies show that interaction between the (Ru-bpy-phen)⁺² and the host CNTs depends on the tube diameter while the chirality doesn’t affect significantly on the binding nature of respected complex. We have also investigated the influence of non-local dispersion interactions (vdW) and temperature on the stability and electronic structure of the considered system. Results obtained from the ab initio MD simulations showed that increasing the temperature can affect the distance between C and N atoms in the linkage position. The charge analysis indicates the existence of remarkable charge transfer between (Ru-bpy-phen)⁺² as donor and fCNTs as acceptor moieties in the isolated molecule. In the presence of vdW forces and at higher temperature, the charge transfer was decreased but the direction of transferred charge remains unchanged.     

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.     

The Application of Infrared Spectra to Structural Problems in Copper(II) Complexes of 2,2′-Bipyridine

The infrared spectra of the complexes [Cu(bipy)₃] (C10₄)^2′ [Cu(bipy)₂] (C10₄)₂, [Cu(bipy)₂I]I, [cu(bipy)₂I] C10₄ and [Cu(bipy)(C10₄)₂] (bipy - 2,2′-bipyridine) are discussed in relation to their known or probable structures. Evidence for tetragonal distortion of [Cu(bipy)₃]₂₊ but not [Cu(phen)₃]₂₊ (phen = 1, 10-phenanthroline) is adduced.     

Synthesis and Spectral Studies of Novel Co(II), Ni(II), Cu(II), Cd(II), and Fe(II) Metal Complexes with N-[5′-Amino-2,2′-bis(1,3,4-thiadiazole)-5-yl]-2-hydroxybenzaldehyde Imine (HL)

Co(II), Ni(II), Cu(II), Cd(II), and Fe(II) complexes with Schiff base derived from 2-amino-5-(2-amino-1,3,4-thiadiazolyl)-1,3,4-thiadiazole (1) and salicylaldehyde have been prepared. The ligand and its complexes have been characterized by IR, ¹H NMR spectra, elemental analyses, magnetic susceptibility, UV-Vis. and thermogravimetry–differential thermal analysis (TGA-DTA). The analytical data show 1:2 metal-to-ligand ratio for Co(II), Ni(II), Cd(II), and Fe(II) and 2:2 metal-to-ligand ratio for Cu(II) complexes. The suggested structures for the N-[5′-Amino-2,2′-bis(1,3,4-thiadiazole)-5-yl]-2-hydroxybenzaldehyde Imine (HL) complexes of Fe(II), Co(II), and Cd(II) are octahedral, for the Ni(II) complex is tetrahedral, and for the Cu(II) complex is square-planar     

Spectrophotometric determination of copper(II) in pharmaceutical,biological and water samples by 4-(2′-benzothiazolylazo)-salicylic acid

A highly sensitive method is proposed to determine copper(II) ions by forming a stable complex through their interaction with 4-(2′-benzothiazolylazo)-salicylic acid (BTAS) at room temperature and pH of about 5.0. The complex gave a maximum absorption at λ = 485 nm with a molar absorptivity coefficient of 2.35·10⁴ l/(mol·cm). The linear range for the copper determination is 0.63–5.04 mg/l. The method can be applied to determine copper ions in different biological specimens like some drugs and water samples.     

Magnetic properties of crystals of the molecular complex between fullerene C60 and an organic donor 9,9′-trans-bis(telluraxanthenyl)

The EPR and static magnetic susceptibility of the crystalline molecular complex between fullerene C60 and an organic donor 9,9′-trans-bis(telluraxanthenyl) (BTX) have been measured as functions of temperature. At temperatures T above 130 K, the samples exhibit anomalously high magnetic susceptibility exceeding the values calculated under the assumption that each molecule bears one paramagnetic spin 1/2. A very intense magnetic resonance signal is also observed in the samples in the region of high g factors (g>4.5). This allows the suggestion that the samples under study possess ferromagnetism (or superparamagnetism). The EPR signal and magnetic susceptibility sharply decay almost to zero as the temperature decreases below 100–120 K. It is supposed that electron transfer from donor molecules BTX to C60 molecules takes place at temperatures above 110 K. This electron transfer generates electron spins in the system, whereas the anomalously high magnetism is due to ferromagnetic correlations in the system of these spins.     

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     

EPR investigations of Cu(II) complexes with 5′-CMP and 5′-GMP

Electron paramagnetic resonance investigation of the Cu(II) complexes with guanosine-5′-monophosphate (5′-GMP) and cytidine-5′-monophosphate (5′-CMP) shows the affinity of the Cu(II) ion to interact with the base and the phosphate group. The different modes of the coordination of the metal ion at the nucleotide and the water molecules lead to octahedral species, distorted by dynamical Jahn-Teller effect (g₀ = 2.106) for the Cu(II)-5′-CMP complex and rhombically distorted (g₁ = 2.358, g₂ = 2.126, g₃ = 2.068) or tetragonally distorted (g_∥^′ = 2.299, g_⊥^′ = 2.126) for the Cu(II)-5′ -GMP complex. The compound with 5′-CMP presents also a more stable in time square-planar species (g_∥ = 2.265, A_∥ = 162 G, g_⊥ = 2.076). The local symmetry changes in aqueous solution by coordination of water molecules.     

Synthesis, Characterization, and Luminescence Spectroscopic Accessibility Studies of tris(2,2′-Bipyridine)Ruthenium(II)-Labeled Inorganic-Organic Hybrid Polymers

The modified tris(2,2-bipyridine)ruthenium(II) complex 2 was anchored via a sol-gel process to different polysiloxane matrices to give a series of novel inorganic–organic hybrid polymers. One of the bipyridine ligands of 2 was provided with a long-chain spacer carrying a triethoxysilyl function (T group) at the end, which enables almost free mobility of the transition metal center. The polymers were swollen in several organic solvents of different polarity to investigate the luminescence behavior in the presence of quencher molecules. The luminescence of 2 was quenched using anthracene and atmospheric oxygen in appropriate concentrations of 5 · 10^–4 to 5 · 10^–3 and 3 · 10^–3 M, respectively. The luminescence behavior of 2 was determined by steady-state and time-resolved luminescence experiments. Translational mobilities of molecular species dissolved in the liquid phase were investigated by the kinetics of luminescence quenching after laser excitation. Both the translational mobility of anthracene and atmospheric oxygen, specified with the rate constant k₂ and the percentage of accessible luminescent centers were determined. Translational mobilities and the accessibility for anthracene and atmospheric oxygen in hybrid materials are significantly higher than in conventional Q type polysiloxanes.     

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.     

Characterisation of geometric isomers of europium chlorides with 2,2′-bipyridine based on X-ray diffraction,luminescence and quantum chemical data

A low-temperature high-resolution luminescence study of the EuCl₃bpy₂(H₂O) _n isomers has been carried out. The Eu³⁺ luminescence spectra of all geometric isomers were recorded over the spectral range which includes transitions from the ⁵D₀ excited state to the ⁷F_0–4 ground state manifolds and from the ⁵D₁ excited state to the ⁷F_0–2 ground state manifolds. Analysis of the Eu³⁺ transitions observed in the luminescence spectra shows that the Eu³⁺ ion occupies a spectroscopic site symmetry that approaches a C_{2 v} symmetry with distortion towards C₂ or lower symmetry. The structural features and distortions of the Eu³⁺ coordination polyhedron in these geometric isomers were described based on the X-ray crystallographic data as well. The splitting patterns and energies found of the ⁷F_0–4 manifolds have been used to calculate the crystal field parameters (CFPs) of the Eu³⁺ ions in these geometric isomers. In addition the mutual influence of the ligands as well as the relative stability of geometric isomers of the [EuCl₃bpy₂(H₂O)₂]⁺ cation in the gas phase was analyzed within DFT calculations.     

Synthesis and Effect of Ammonium 2,2′-Methylene-bis-(4,6-di-t-Butylphenylene) Phosphate as Nucleating Agent of Poly(Propylene)

A nonmetallic organophosphate salt, ammonium 2,2′- methylene-bis-(4,6-di-t-butylphenylene) phosphates (An), was synthesized via a simple method, and its application in iPP as a nucleating agent was investigated. Differential scanning calorimetry (DSC) result showed the melting temperature of An was 262°C, and SEM (scanning electron microscopy) observations indicated that its crystallization morphology was lamellar shape with a quite smooth surface. The crystallization behavior of nucleated isotactic poly(propylene) (iPP) containing An demonstrated that An can effectively raise the crystallization peak temperature and reduce the spherulite size, resulting in obviously improved strength and transparency. The tensile and flexural strength of iPP nucleated with An was increased by 11% and 32%, respectively. The haze value of iPP/An was decreased from 36.7% to 15.5%. These results revealed that this organophosphate ammonium salt can be used as an effective nucleating agent of iPP and provides a new organophosphate salt type nucleating agent for polymers.     

Spectral properties of naphthalimide dyes mixed with 4-heptyl-4′-cyanobiphenyl (7CB) in Langmuir-Blodgett films

Langmuir-Blodgett (LB) films formed of some fluorescent dyes, namely derivatives of 4-aminonaphthalimide, and their binary mixtures with the liquid crystal 4-heptyl-4′-cyanobiphenyl (7CB) have been studied. The electronic absorption and fluorescence spectra were recorded. On the basis of these spectra, the spectral properties of the dyes and the intermolecular interactions in ultrathin ordered films were determined. The conclusions about the tendency to the creation of aggregates by dye molecules in LB films have been drawn. The measurements of absorption by using linearly polarised light have allowed us to determine the arrangement of the dye and liquid crystal molecules on the air-solid substrate interface.     

Enhancement of electronic,photophysical and optical properties of 5,5′-Dibromo-2,2′-bithiophene molecule: new aspect to molecular design

The aims of this study were to enhance electronic, photophysical and optical properties of molecular semiconductors. For this purpose, the isomers of the B-doped molecule (5,5′-Dibromo-2,2′-bithiophene) have been investigated by density functional theory (DFT) based on B3LYP/6-311++G** level of theory. The isomers were first calculated using kick algorithm. The most stable isomers of the B-doped molecule are presented depending on the binding energy, fragmentation energy, ionization potential, electron affinity, chemical hardness, refractive index, radial distribution function and HOMO-LUMO energy gap based on DFT. Ultraviolet-visible (UV–vis) spectra have been also researched by time-dependent (TD) DFT calculations. The value of a band gap for isomer with the lowest total energy decreases from 4.20 to 3.47 eV while the maximum peaks of the absorbance and emission increase from 292 to 324 nm and 392 to 440 nm with boron doped into 5,5′-Dibromo-2,2′-bithiophene. Obtained results reveal that the B-doped molecule has more desirable optoelectronic properties than the pure molecule.     

Highly efficient simultaneous ultrasonic-assisted adsorption of Pb(II), Cd(II), Ni(II) and Cu (II) ions from aqueous solutions by graphene oxide modified with 2,2′-dipyridylamine: Central composite design optimization

In present work, a graphene oxide chemically modified with 2,2′-dipyridylamine (GO-DPA), was synthesized by simple, fast and low-cost process for the simultaneous adsorption of four toxic heavy metals, Pb(II), Cd(II), Ni(II) and Cu(II), from aqueous solutions. The synthesized adsorbent was characterized by FT-IR, XRD, XPS, SEM and AFM measurements. The effects of variables such as pH solution, initial ion concentrations, adsorbent dosage and sonicating time were investigated on adsorption efficiency by rotatable central composite design. The optimum conditions, specified as 8 mg of adsorbent, 20 mg L⁻¹ of each ion at pH 5 and short time of 4 min led to the achievement of a high adsorption capacities. Ultrasonic power had important role in shortening the adsorption time of ions by enhancing the dispersion of adsorbent in solution. The adsorption kinetic studies and equilibrium isotherms for evaluating the mechanism of adsorption process showed a good fit to the pseudo-second order and Langmuir model, respectively. The maximum adsorption capacities (Q_m) of this adsorbent were 369.749, 257.201, 180.893 and 358.824 mg g⁻¹ for lead, cadmium, nickel and copper ions, respectively. The removal performance of adsorbent on the real wastewater samples also showed the feasibility of adsorbent for applying in industrial purposes.