The intermolecular pair potential of argon and third virial coefficients

Triplet-triplet (T-T) absorption spectra were measured in the wave-number region between 5000 and 30 000 cm^-1 for the 1,2,4,5-tetracyanobenzene complexes with toluene, mesitylene, durene, and hexamethylbenzene. From the analysis of the observed T-T absorption spectra, with the aid of theoretical considerations based on the interaction among zero-order charge-transfer and locally excited triplet states, the assignment was made and the nature of the lower triplet states of the complexes was clarified. We conclude that the lowest zero-order charge-transfer triplet state and the lowest zero-order locally excited triplet states are close to each other for the complexes, and the charge-transfer character of the lowest state changes from 81 to 15 per cent by changing the electron donor from hexamethylbenzene to toluene.     

Spectrophotometric and E.P.R. study of TCNE charge-transfer complexes

Liquid state charge-transfer complexes formed from the strong acceptor tetracyanoethylene (TCNE) and four donors of like donor properties are studied by spectrophotometric and E.P.R. techniques. If the enthalpy of complex formation ΔH is sufficiently large, the triplet state of the complex ³C will be appreciably populated thermally during complex formation. The E.P.R. signal of the TCNE anion promptly arises because of a dissociation of ³C, reaches a maximum, and then follows second-order decay kinetics. The higher the dielectric constant of the donor, the slower the decay rate. The initial intensity of the E.P.R. signal is proportional to the original TCNE concentration in the donor-solvent. Reversible photoinduced TCNE anions are formed by irradiating the complexes in the charge-transfer band. The relationship between the prompt and photoinduced E.P.R. signals is shown. Singlet-triplet separation energies are estimated.     

Triplet-triplet absorption studies on related heterocyclic molecules

A study of the triplet-triplet (T-T) absorption spectra of a series of aromatic heterocyclic molecules in EPA glass at 77°K has been carried out in the region 11 000–27 000 cm^?1 using a steady cross illumination technique. Two transitions have been observed in each of dibenzofuran and dibenzothiophene and assigned as $\text{ππ}{}^1\text{← ππ}{}^1$ in nature. A similar assignment has been made for the two transitions observed in 5,6-benzoquinoline and the one transition observed in 7,8-benzoquinoline. A single transition has been observed in phthalazine. Measurements of the decay of T-T absorption have been carried out and, in all cases, the correspondence with the phosphorescence lifetimes verified the triplet nature of the observed absorptions. A comparison of the information obtained from T-T spectra with phosphorescence and/or ESR data is made in order to demonstrate how T-T spectra can be used to aid in the understanding of the properties of the lowest triplet state. Thus for dibenzofuran and dibenzothiophene, a comparison of upper triplet state energies suggests that the heteroatoms do not provide effective conjugation with the hydrocarbon rings in the lowest triplet state. For the benzoquinolines, the T-T spectra suggest a close analogy with the triplet state properties of phenanthrene although 4-aza substitution (7,8-benzoquinoline) seems to produce an increased perturbation of the $\text{ππ}{}^1$ states by $\text{nπ}{}^1$ states as compared with 1-aza substitution (5,6-benzoquinoline).     

Manifestation of nonplanarity effects and charge-transfer interactions in spectral and kinetic properties of triplet states of sterically strained octaethylporphyrins

Properties of the triplet states of octaethylporphyrins with the steric hindrance (free bases and Pd complexes) are studied by the methods of stationary and kinetic spectroscopy in the temperature range from 77 to 293 K. The mono-mesophenyl substitution results in a decrease in the quantum yield and shortening of the phosphorescence lifetime of Pd complexes by 250–3500 times in degassed toluene at 293 K. The phosphorescence quenching is caused by nonplanar dynamic conformations of the porphyrin macrocycle in the T ₁ state, which also lead to the appearance of new bands at λ～1000 nm in the T-T absorption spectra. As the number of meso-phenyls (Pd-octaetyltetraphenylporphyrin) increases, the quantum yield of phosphorescence further decreases (<10^?5) at 293 K, the lifetime of the T ₁ state shortens (<50 ns), and the efficiency of the singlet oxygen generation abruptly decreases (<0.01). The intense bathochromic emission of this compound at 705 nm with a lifetime of 1 ms at 77 K is assigned to the phosphorescence of a nonplanar conformation. Upon meso-orthonitrophenyl substitution, the quenching of phosphorescence of Pd complexes (by more than 10⁴ times at 293 K) is caused by direct nonadiabatic photoinduced electron transfer from the T ₁ state to the nearest charge-transfer state with the probability k _et ^T =(1.5–4.0)×10⁶ s^?1. The induced absorption of ortho-nitro derivatives in the region between 110 and 1400 nm is caused by mixing of pure ππ* states with charge-transfer states.     

Organic light‐emitting materials based on iridium(III) complexes bearing phenanthroimidazole ligands

We present the elegant synthesis and the photophysical and electroluminescent properties of a series of cyclometalated iridium(III) complexes [Ir(PPI)₂(pic), PPI: 1,2‐diphenyl‐1H‐phenanthro[9,10‐d]imidazole; pic: picolinic acid]. The Ir(PPI)₂(pic) complexes showed characteristic phosphorescence with an emission range of 556–579 nm and a high quantum efficiency with microsecond lifetimes. The strongly allowed phosphorescence in these complexes is the result of significant spin–orbit coupling of the Ir center. All bis(PPI) derivatives exhibit intense triplet metal‐to‐ligand charge transfer (MLCT) photoluminescence in the fluid solutions at room temperature. The impact of different solvents, substituents on the phenanthroimidazole ligands and complex concentrations upon their emissive behavior have been examined and demonstrate that their emission energies can be systematically modified. Weak bands located at longer wavelength have been assigned to the ¹MLCT ← S₀ and ³MLCT ← S₀ transitions of iridium complexes. Application of the ³MLCT excited state of the [Ir(PPI)₂(pic)] materials in organic light‐emitting devices are described. Copyright © 2014 John Wiley & Sons, Ltd.     

Spectroscopic Study of Luminescence and Energy Transfer of Binary and Ternary Complexes of Rare Earth with Aromatic Carboxylic Acids and 1,10-Phenanthroline

A series of rare earth (Gd, Eu, Tb) complexes with different substituent group carboxylic acids (ortho-hydroxylbenzioc acid, ortho-aminobenzoic acid and ortho- methoxy benzoic acid) and 1,10-phenanthroline were synthesized. The spectroscopic studies of the photophysical properties such as luminescence properties, energy match and intramolecular energy transfer were carried out. The lowest triplet state energies of ligands and the intramolecular energy transfer efficiencies were determined with the measurement of low phosphorescence spectra and lifetimes of Gd complexes.     

Radiationless intermolecular energy transfer with participation of acceptor excited triplet states

Radiationless energy transfer between like and unlike molecules has been experimentally studied under conditions where acceptor molecules have been excited to the triplet state Homogeneous singlet-triplet-triplet migration has been discovered in highlyconcentrated chlorophyll “a” and pheophytin “a” solutions in castor oil at 183 K by measuring the variation of pigment relative quantum yields of fluorescence and triplet state formation as a function of exciting pulse intensity. Heterogeneous single-triplet-triplet energy transfer has been observed in solid solutions of different complex organic molecules (perylene + phenanthrene, Na-fluorescein+chlorophyll “a”, pyrene+Mg-phthalocyanine) as the fluorescent donor state quenching in the presence of acceptor triplet-excited molecules. Primary emphasis is placed on a direct observation of the effect of energy transfer on the excited-state lifetime of the donor. The benzophenone phosphorescence quenching (shortening of phosphorescence lifetime) in the presence of Mg-mesoporphyrin triplet molecules has been found to be caused by the heterogeneous triplet-triplet-triplet energy transfer. Good agreement of the theoretical and experimental results permits us to conclude that all types of observed transfer processes are described by the Förster-Galanin theory for dipole-dipole radiationless energy transfer with no additional assumptions.     

Synthesis and Fluorescence Properties of Lanthanide (III) Perchlorate Complexes with Bis(benzoylmethyl) Sulfoxide

A ligand with two carbonyl groups and one sulfinyl group has been synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, ¹H NMR and UV spectra. The results indicated that the composition of these complexes is REL₅(ClO₄)₃·3H₂O (RE = La(III), Pr(III), Eu(III), Tb(III), Yb(III), L = C₆H₅COCH₂SOCH₂COC₆H₅). The fluorescent spectra illustrate that both the Tb (III) and Eu (III) complexes display characteristic metal-centered fluorescence in solid state, indicating the ligand favors energy transfer to the excitation state energy level of them. However, the Tb (III) complex displays more effective luminescence than the Eu (III) complex, which is attributed to especial effectively in transferring energy from the average triplet energy level of the ligands (T) onto the excited state (⁵D₄) of Tb (III) than that (⁵D₀) of Eu (III), showing a good antenna effect for Tb(III) luminescence. The phosphorescence spectra and the relationship between fluorescence lifetimes and fluorescence intensities were also discussed.     

Heavy-atom effect on radiative and radiationless transitions in charge-transfer complexes

The quantum yields of fluorescence and phosphorescence and decay times of fluorescence were measured for a series of charge-transfer complexes of hexamethylbenzene (an electron donor) with various electron acceptors containing heavy (halogen) atoms and the rate constants of different radiative and radiationless transitions were determined. It was found that radiative T₁ → S₀ transition, i.e. the phosphorescence, is strongly enhanced by the heavy-atom effect. The mechanism of the heavy-atom enhancement of charge-transfer phosphorescence is discussed and it is concluded that increasing spin- orbit mixing of radiative T₁ → S₀ charge-transfer transition with singlet-singlet, locally excited transition of acceptor molecule is responsible for the observed effects.     

Mechanism for quenching of the luminescence of 9,10-anthraquinone vapor by oxygen

The fluorescence of 9,10-anthraquinone, 1-aminoanthraquinone, 1,4-diaminoanthraquinone, and 1,5-diaminoanthraquinone is not quenched by oxygen because the singlet-triplet energy difference in these compounds is less than the energy needed for excitation of the triplet state of oxygen to the singlet state. Luminescence of 9,10-anthraquinone is quenched because it is mainly phosphorescence, for which the singlet-triplet difference is sufficient for quenching by a mechanism involving singlet oxygen formation. The weak fluorescence of 9,10-anthraquinone is not quenched. The resistance of the fluorescence of 9,10-anthraquinone vapor to quenching by oxygen and the quenching of its phosphorescence explain the different effects of oxygen on the luminescence of α-substituted and β-substituted anthraquinones known from the literature, and indicate that their singlet excited state cannot convert triplet oxygen to singlet oxygen. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 79–4, January–February, 2008.     

Phosphorescence from an EDA complex with nitrobenzene as an electron donor

Excitation of the EDA complex formed between the donor, nitrobenzene, and the acceptor, boron trichloride, gives rise to a phosphorescence centered at 579 nm with a quantum yield of 2.3 ± 0.1 × 10^-3, which is assigned to the charge transfer triplet state of the complex. The formation constant of the complex was determined to be 50 ± 15 M^-1 at 77 K. Photochemical quantum yield data at room temperature for the photoreduction of nitrobenzene as the nitrobenzene-boron trichloride complex to nitrosobenzene indicates reactivity increasing with boron trichloride concentration. A comparison of the phosphorescence and electrochemical data for the 1:1 EDA complexes between nitrobenzene, benzophenone and pyridine and boron trichloride predicts that the oxidation potentials for nitrobenzene and benzophenone are +1.32 and +1.63 V vs. the saturated calomel electrode, respectively, and reflect the availability of a non-bonding electron pair for complexation.     

Luminescence properties of some platinum (II) complexes. Counter-ion and molecular geometry effects

Reflectance and luminescence spectra, and emission lifetimes of 14 charged and neutral Pt (II) complexes in the solid crystalline state are reported. The lifetimes (in the range of some tens of microseconds) indicate that the emissions are due to a spin-forbidden process. On the basis of spectral correlations, the phosphorescence is tentatively identified as due to the lowest d-d ligand field transition when the bonding of the ligand is essentially σ in character, and to a π1 → d charge-transfer transition for those complexes in which the ligands themselves have π orbital systems. Both the radiative (k_r) and non-radiative (k_n) rate constants are sensitive to changes in molecular geometry (cis, trans isomers) and counter-ions. Assuming unitary efficiency for the intersystem crossing to the emitting state, the counter-ion appears to predominantly affect k_n through vibrational coupling of the chromophore with the lattice. For the cis forms, both k_r and k_n are affected in a complex manner, with metal-metal interactions playing an important role. For the trans forms, however, the constancy of the quantum yield with respect to temperature suggests that k_n is negligible in comparison to k_r, and therefore the trans chromophores behave as isolated systems within the crystalline lattice.     

The role of environment in the nonradiative relaxation of the triplet state of naphthalene derivatives in solid solutions at 77 K

The nonradiative relaxation of the triplet states of oxy-and amino-derivatives of naphthalene and conjugated ions is studied by luminescent and kinetic methods (measurements of the phosphorescence decay and of phosphorescence excitation and phosphorescence spectra) in solid solutions of ethanol-h ₆, ethanol-d ₆, and mixtures of toluene-h ₈ with piperidine-h ₁₁ at 77 K. It is found that, along with intramolecular factors, a microsolvate surrounding a molecule or an ion substantially affects the nonradiative relaxation. The contribution of this factor in ethanol increases in the series cation-polar molecule-anion and in mixtures of toluene with piperidine—with increasing piperidine concentration. The results are interpreted assuming the inductive-resonance dipole-dipole transfer of the triplet energy to the dipole acceptors of intramolecular bonds and bonds with molecules of the environment. The relative arrangement of hydrogen atoms of OH groups of ethanol molecules in microsolvates of cations and anions estimated using the inductive-resonance model agrees with the difference in the structure of solvates of oppositely charged ions, which is caused by the electrostatic charge-dipole interaction and the distribution of the electron density in the ground state of the corresponding emitting center. The inductive-resonance model was used for studying the features of solvation processes involving polar molecules. It is shown that the difference between the structures of microsolvates of 2-oxy-naphthalene molecules in solvents with close dipole moments (ethanol and piperidine) is mainly caused by the different ability of these solvent molecules to form associates. The structure of microsolvates of oxy-derivatives of naphthalene in the associated amphoteric solvent is found to depend on the number and position of substituents. In oxy-derivatives of naphthalene with spatially separated OH groups in ethano-d ₆, deuteroexchange occurs in both substituents, whereas in the naphthalene derivative with adjacent OH groups this occurs only in one of the groups. Comparison of the phosphorescence spectra of hydrogen-bond complexes and proton-transfer complexes in nonpolar solvents at 77 K revealed the existence of molecular naphthol entities in the triplet state that were formed from ionized entities in the singlet state.     

A comparative study of the solid-matrix phosphorescence of heterocyclic aromatic amines in glucose glasses as a function of temperature

Solid-matrix phosphorescence intensities and lifetimes were obtained for 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) and 2-amino-9H-pyrido[2,3-b]indole (AαC) as a function of temperature from room temperature to 93 K. The two solid matrices employed were glucose glasses prepared with crystalline glucose and a glucose melt, both with and without a heavy-atom salt, NaI. In general, the phosphorescence intensities and lifetimes of PhIP increased as the temperature was lowered. The intensity-to-lifetime ratios showed that the triplet state formation efficiency of PhIP changed as a function of temperature for glasses prepared without NaI. This illustrated that the phosphorescence intensity was a function of both triplet state formation efficiency and phosphorescence lifetime. For the glasses prepared with NaI, the triplet state formation efficiency of PhIP remained essentially constant with temperature. Thus, the phosphorescence intensity was only a function of phosphorescence lifetime. The phosphorescence intensity for AαC was essentially the same at room temperature and at 93 K in glasses prepared with 10% NaI. Thus, this heavy-atom salt/glucose system was able to achieve the maximum phosphorescence signal at room temperature. Using the phosphorescence lifetimes as a function of temperature, activation energies for the phosphors in the glasses were calculated. The phosphorescence lifetime data fit a biexponential equation and two activation energies were obtained. The lower activation energy was related to low-frequency vibrations in the glucose matrix, and the higher activation energy was related to β-relaxation processes that occur in glucose glasses.     

Substituent effects on the triplet-triplet absorption spectra of coumarin and its derivatives

Preliminary work on the triplet-triplet (T-T) absorption of coumarin and two of its 4-hydroxy substituted derivatives is extended to four additional substituted coumarins in order to investigate substituent effects on T-T absorption in these molecules. A steady cross Illumination technique is used in EPA glass at 77° K. Measurements of the decay of T-T absorption are carried out with a flash technique and a comparison made with phosphorescence lifetimes to verify the triplet nature of the absorption. The observed T-T spectra show a marked dependence on the presence and position of hydroxy substitution. An explanation is developed based on the mixing of $\text{nπ}{}^1$ character into the lowest $\text{ππ}{}^1$ triplet state. The effect of methyl substitution is also investigated and, although it leads to relatively small changes in the T-T spectra, the results suggest that it plays a role in the susceptibility of the molecules to photochemical change.     

Spectroscopic Study on the Photophysical Properties of Lanthanide Complexes with Long Chain Mono-Docosyl Phthalate

Ortho phthalic anhydride was modified with long chain alcohol (1-docosanol) to its corresponding monodocosyl phthalate (22-Phth). Subsequently, three novel lanthanide (Eu³⁺, Tb³⁺, and Dy³⁺) complexes with the long chain monodocosyl phthalate were synthesized and characterized by elemental analysis and Infrared spectra. The photophysical properties of these complexes were studied in detail with ultraviolet-visible absorption spectra, low temperature phosphorescence spectra and fluorescent spectra. The triplet state energy of 22-Phth was determined to be around 25,000 cm⁻¹ from the maximum phosphorescent peak at 400 nm, suggesting 22-Phth is suitable for the sensitization of the luminescence of Eu³⁺, Tb³⁺, and Dy³⁺. The fluorescence excitation and emission spectra for these lanthanide complexes of the three ligands take agreement with the above predict from energy match principle.     

Synthesis and Study of the Photophysical Properties of a New Eu<Superscript>3+</Superscript> Complex with 3-Hydroxypicolinamide

This work reports on the synthesis and characterization of a new complex of Eu³⁺ with the 3-hydroxypicolinamide ligand (Hhpa). Here we present an approach for obtaining bis[2-carbamoyl(κO)pyridin-3-olato(κO’)] lanthanide complexes, which were characterized through elemental analysis, thermal analysis, infrared and photoluminescence spectroscopies (emission, excitation, luminescence lifetimes, quantum efficiencies, Judd-Ofelt parameters and quantum yields). Although hpa can act as a bidentate ligand in different conformations, the results attest for the occurrence of a unique coordination site of low symmetry for the Eu³⁺ ions, in which two anionic hpa ligands coordinate the cations through an O/O chelating system. The phosphorescence of the synthesized gadolinium complex provides the energy of the triplet state, which is determined to be at 20,830 cm^-1 over the ground state. This makes the Hhpa ligand very adequate for sensitizing the Eu³⁺ luminescence, which leads to a very efficient antenna effect and opens a wide range of applications for the complex in light emitting organic-inorganic devices.     

The influence of Förster energy transfer on spectral and kinetic characteristics of phosphorescence and thermally activated delayed fluorescence of acriflavine in a polyvinylalcohol matrix

Spectral and kinetic characteristics of thermally activated delayed fluorescence (TADF) and phosphorescence of acriflavine in polyvinylalcohol films have been investigated. It was shown that TADF and phosphorescence decay times decrease due to fluorescence resonance energy transfer (FRET) as the concentration of the dye molecules increases. The luminescence spectra of the concentrated solutions are bathochromic shifted with respect to that of the deluted ones. Moreover, TADF and phosphorescence spectra of the concentrated solutions shift to the higher frequency region as emission decays. These effects are determined by the correlation between FRET direction and the heterogeneity of the triplet state lifetimes. Numerical simulations of the spectral and kinetic characteristics of TADF and phosphorescence were made by means of Monte-Carlo integrations, and results were compared with experimental data.     

N.M.R. spectra of oriented molecules

The phosphorescence spectra of anthracene-h₁₀ and -d₁₀ have been studied in a number of glasses and crystalline matrices. The line widths are very matrix dependent and they range from about 150 cm^-1 to 1 cm^-1 in n-heptane. There is a correlation between the line width and the wavenumber position of the origin. A study of the relative intensities of fluorescence and phosphorescence from various sites in Shpolskii matrices has shown that the intersystem crossing rate is site dependent. It is postulated that this involves the relative energies of the singlet state and a triplet state, nearly degenerate with it, which are site dependent.     

Synthesis and Fluorescence Properties of Lanthanide (III) Perchlorate Complexes with Naphthyl-Naphthalinesulphonylpropyl Sulfoxide

A ligand with double sulfinyl groups, naphthyl-naphthalinesulphonylpropyl sulfoxide(dinaphthyl disulfoxide, L), was synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DTA, ¹HNMR and UV spectra. The composition of these complexes, were RE₂(ClO₄)₆·(L)₅·nH₂O (RE = La, Nd, Eu, Tb, Yb, n = 2 ∼ 6, L = C₁₀H₇SOC₃H₆SOC₁₀H₇). The fluorescent spectra illustrated that the Eu (III) complex had an excellent luminescence. It was supposed that the ligand was benefited for transferring the energy from ligand to the excitation state energy level (⁵D₀) of Eu (III). The Tb (III) complex displayed weak luminescence, which attributed to low energy transferring efficiency between the average triplet state energy level of ligand and the excited state (⁵D₄) of Tb (III). So the Eu (III) complex displayed a good antenna effect for luminescence. The phosphorescence spectra and the relationship between fluorescence lifetime and fluorescence intensity were also discussed.