External heavy atom effect on the triplet state of aromatic hydrocarbons: IV. Fluorene,triphenylene-d12 and coronene

The phosphorescence decay functions and spectra of ethanol solutions of triphenylene-d₁₂, coronene and fluorene were observed in the presence of different KI concentrations at 77 K. The analysis of the dependence of phosphorescence (T₁ → S₀) rate constant, k_PT, and intersystem crossing (T₁ ? S₀) rate constant, k_GT, on triplet energies E_T of aromatic molecules and on the distance between the heavy atom and the aromatic molecule show that the external heavy atom effects on k_PT and k_GT are essentially of the second and third order, respectively. The phosphorescence spectra of triphenylene and coronene show the presence of the third order contributions in the radiative transition, which involves the second triplet state of aromatic molecule.     

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.     

Studies of the temperature dependence of the phosphorescence spectra and decay rates of aromatic carbonyl molecules in mixed organic crystals

The temperature dependence of the phosphorescence spectra, decay rates and the S ₀ → T ₂(³ nπ*) absorption spectra were studied for aromatic carbonyl molecules in mixed organic crystals. The energy separation, ΔE_T , between the ³ ππ* lowest excited triplet (T ₁) states and the higher ³ π ^* states (T ₂) was estimated for several systems from the temperature dependence of the phosphorescence spectra and decay rates. It was found that the decay rates of the aromatic carbonyl molecules in the mixed crystal systems studied are determined by (1) thermal population to the ³ nπ* states and (2) increased radiationless transition rates at higher temperatures.     

Nonradiative deactivation of the lowest triplet state of naphthalene and its hydroxy derivatives at 77 K

The validity of an inductive resonance theory of energy transfer from the T ₁→S ₀ transition dipole to overtone vibrations of molecular groups containing H and D atoms is experimentally tested for a series of compounds whose conjugation systems are similar in size. To this end, by using kinetic, spectral, and luminescent methods (measurements of the phosphorescence decay times, phosphorescence spectra, ratios between the quantum yields of phosphorescence and fluorescence at 77 K, total quantum yields of fluorescence at 293 K, and ratios between the quantum yields of fluorescence at 293 and 77 K), the deactivation processes of the lowest excited T ₁ and S ₁ states of seven emitting centers (naphthalene, its hydroxy and dihydroxy derivatives, and their monoanions) in solutions in ethanol-h ₆, ethanol-d ₆, and their 2: 1 mixtures with diethyl ether are studied. For all the compounds studied, the rate constants k _r of the radiative T ₁→S ₀ transition and the changes in the overlap integrals of the spectra of phosphorescence and absorption of overtones of CH stretching vibrations are determined. The rate constants of energy transfer k _dd(CH) from the T ₁→S ₀ transition dipole to the stretching vibrations of the CH bonds are calculated without regard for the changes in the localization and orientation of this transition dipole in the compounds under study. The contribution of an individual CH group k _nr(CH) to the total rate constant of nonradiative deactivation of the T ₁ state averaged over the CH groups of the naphthalene ring system is ascertained. A good correlation between the changes in the constants k _nr(CH) and k _dd(CH) in the series of the hydroxy derivatives of naphthalene is found, which is indicative of the inductive resonance mechanism of the energy degradation of the T ₁ state. The deviations from proportionality between the changes in these constants upon passing from naphthalene to its hydroxy derivatives, which correlate with a marked increase in the radiative constant k _nr of the hydroxy derivatives in comparison with naphthalene, indicate changes in the strength and localization of the T ₁→S ₀ transition dipole moment and in its orientation with respect to the plane of the molecule that occur due to introduction of a heteroatom, oxygen, whose lone pair of electrons enters into conjugation with the πelectrons of the naphthalene ring system.     

Temperature dependence of the emission spectra of p-benzoquinone in a p-dichlorobenzene matrix

Emission and excitation spectra of p-benzoquinone have been measured in a partially translucent p-dichlorobenzene host matrix at different temperatures from 77 up to 323 K. Successive occurrence of the T₁(n,π^?) and T₂(n,π^?) phosphorescence and S₁(n,π^?) fluorescence has been observed for p-benzoquinone upon increasing temperature. The S₁–T₂ and T₂–T₁ energy separations determined from the temperature dependence of the emission intensities agreed well with those obtained from the locations of the T₁ and T₂ phosphorescence and S₁ fluorescence origins. Occurrence of the emission from S₁ and T₂ is brought by the thermal population from the T₁ state. The symmetries of the T₁ and T₂ states were determined to be B_1g and A_u, respectively, based on the spectral data.     

Kinetics of long-lived luminescence of eosin in Langmuir-Blodgett films

The spectral and kinetic properties of photoluminescence of mixed Langmuir-Blodgett (LB) films of eosin decyl ether and palmitic acid on a solid substrate are studied. The electronic absorption and fluorescence spectra of the films are identical to the spectra of the dye in ethanol. An increase in the dye concentration in a monolayer results in the appearance of a dimer absorption band, quenching of fluorescence of monomers, and the red shift of the spectral bands. At 90 K, the distinct phosphorescence and delayed fluorescence bands of LB films were observed. The decay kinetics of phosphorescence and delayed fluorescence is nonexponential. It is shown that the decay curve of delayed fluorescence is determined by triplet-triplet annihilation (TTA) and T ₁→S₁ triplet-singlet intersystem crossing (IS). The initial nonexponential phosphorescence decay is caused the dominant contribution of TTA to the decay of triplet molecules. The experimental data are interpreted based on the mechanisms of exchange-resonance and inductive-resonance annihilation.     

Conformational dynamics and spin-orbit interactions in a series of sterically hindered porphyrins in the lowest triplet state

We have studied the nature and unusual photophysical properties of triplet states of a series of sterically hindered porphyrins (meso-phenyl-substituted derivatives of octamethylporphyrin (PS-OMP)) using quantum-chemical calculations of the parameters that determine the probability of deactivation of the T ₁ state and modeling the T-T absorption spectra. We show that a decrease in the lifetime of the T ₁ state of PS-OMP is related with the enhancement of the channel of nonradiative deactivation (T ₁ → S ₀), which occurs (i) due to the conformational lability in the T ₁ state, as a result of which the energy gap T ₁-S ₀ considerably decreases, and (ii) because of an increase in the matrix element of the spin-orbit interaction due to a change in the hybridization of atoms of the macrocycle as a consequence of its nonplanar distortion. The value of the vibronically induced matrix element of the spin-orbit interaction between the S ₀ and T ₁ states of PS-OMP depends weakly on the type of the conformation and the value and the character of distortion of the porphyrin macrocycle. The conformational lability of PS-OMP clearly manifests itself in the spectra and kinetics of the T-T absorption of these compounds at room temperature and determines the nonmonoexponential character of the phosphorescence decay kinetics in frozen matrices. Using porphin as an example, we have shown that nonplanar distortions of the macrocycle facilitate a decrease in the phosphorescence rate constant at 77 K, which is caused, on the one hand, by an increase in the energy gaps T ₁-S _n and S ₀-T _n and, on the other hand, by an increase in the wavelength of the transition T ₁ → S ₀.     

Excitation of phosphorescence of pyrene implanted into a photoconductive polymer

Methods of populating the lowest excited triplet state T ₁ of pyrene implanted into polystyrene (PS) or photoconductive polymer materials polymethylphenylsilane (PMPS), poly-N-epoxypropylcarbazole (PEPC), and poly-N-vinylcarbazole (PVK) are studied. Photoluminescence was excited in the first electron transition band of pyrene and the above photoconductive polymers. It is found that, at concentrations of 0.05–0.50 mol l^?1, pyrene is effective in quenching the fluorescence of PMPS, PEPC, and PVK but has only a slight effect on the photoemission efficiency of geminate electron-hole pairs. As a result, the phosphorescence of pyrene in photoconductive polymers is excited both by the intersystem crossing from the first excited singlet state (S ₁ ? T ₁) and by the capture of triplet excitons created in the recombination of charge pairs. In addition, in PEPC and PVK, the phosphorescence of pyrene is excited by recombination of a captured hole with an electron. For this reason, the ratio of the quantum yields of phosphorescence and fluorescence of pyrene in photoconductive polymers is much larger than that in PS, wherein the T ₁ state of pyrene is populated by intersystem crossing S ₁ ? T ₁ only.     

Features of dual fluorescence of 1, 2, 3, 4- tetrahydroisoquinoline

In polar and nonpolar solvents, tetrahydroisoquinoline emits S₂ (ππ¹) → S₀ and S₁ (ππ¹) → S₀ dual fluorescence and T₁ (ππ¹) → S₀ phosphorescence on S₂ (ππ¹) ← S₀ excitation. When excited by S₁ (ππ¹) ← S₀ the molecule yields S₁ (ππ¹) → S₀ fluorescence and T₁ (ππ¹) → S₀ phosphorescence in nonpolar solvent but only fluorescence in polar solvents. Probable participation of intermediate S₁ (nπ¹), T₁(nπ¹) states in intersystem crossing and internal conversion processes and its significance in interpreting the results are discussed.     

Spectral manifestations of the splitting of the lowest triplet levels in Pd complexes of nonsymmetric porphyrins

Based on the study of the phosphorescence and phosphorescence excitation spectra of Pd(II) tetramethylporphyrin (PdTMP) and Pd(II) tetramethyldiethylporphyrin (PdTMDEP) in solutions in 2-methyltetrahydrofuran and dodecane in the temperature range 77–283 K, the occurrence of the splitting of the lowest degenerate singlet (S ₁) and triplet (T ₁, T ₂) levels of porphyrin molecules is established. In the absorption of molecules of the compounds studied, two components, S ₁ and S ₂, are revealed in the range of allowed long-wavelength Q(0,0) transitions (530–550 nm) and four components, T ₁–T ₄, are observed in the range of spin-forbidden intersystem crossing transitions S ₀ → T _n (560–670 nm), with all the triplet levels T ₁-T ₄ being located below the S ₁ level on the energy scale. It is shown that an increase in the degree of deformation of the porphyrin macrocycle caused by steric interactions between β alkyls and hydrogen meso atoms is accompanied by an increase in the splitting in the system of singlet levels δE(S ₂–S ₁) from 120 cm^?1 for PdTMDEP to 215 cm^?1 for PdTMP, as well as by an increase in the splitting in the system of triplet levels δE(T ₂–T ₁) from 190 cm^?1 for PdTMDEP to 250 cm^?1 for PdTMP.     

Spectroscopy and dynamics of the excited singlet and triplet states of 2,3-, 2,4- and 2,5-difluorobenzaldehyde vapors

Emission and absorption spectra have been measured for 2,3-, 2,4- and 2,5-difluorobenzaldehyde vapors at different temperatures. The observed emission consists of the T₁(n, π*) phosphorescence accompanied by the weak S₁(n, π*) delayed fluorescence for all the molecules. The vibrational analyses of the emission spectra based on the results of the DFT calculations indicate that the observed emission originates from only the stable (anti) conformer. It is inferred from the temperature dependence of the phosphorescence intensity that the T₁(n, π*) → T₂(π, π*) internal conversion and/or the reverse T₁(n, π*) → S₁(n, π*) intersystem crossing contribute to the decrease in the phosphorescence intensity upon increasing temperature. The obtained spectroscopic data include the Raman spectrum of 2,3-difluorobenzaldehyde.     

Dibaryon resonances with retarded decay

The nonstrange resonances which cannot decay in the NN, NΔ or ΔΔ channels or which can decay in these channels only with the $\text{ls}$ and tensor quark-quark interaction, are presented in the nonrelativistiv quark model with six quarks grouped in two clusters. The GCM calculation gives energies of 3203 MeV, 2540 MeV and 2814 MeV for the resonances (T = 0, S = 0, L = 0), (T = 0, S = 1, L = 1) and (T = 1, S = 0, L = 1), respectively.     

Spectral manifestations of nonplanarity effects in Pd complexes of porphyrins

It is found on the basis of kinetic spectral studies in nonane, dodecane, and vitreous solutions at 77 K (phosphorescence spectra, polarized phosphorescence, decay kinetics, and phosphorescence excitation spectra) that symmetric and nonsymmetric Pd-porphyrins are characterized by the presence of two noninteracting spectrally different long-and short-wavelength forms in the ground state. The existence of the long-wavelength form is associated with the displacement of the central Pd ion from the macrocycle plane, which leads to the formation of the nonplanar “dome” conformation of the porphyrin ligand. In the case of a nonsymmetrically substituted Pd-tetramethyl-diethylporphyrin molecule, the nonplanar conformation of the π-conjugated macrocycle is characterized by the splitting of the triplet state into two components (T ₁ and T ₂, Δν=90 cm^?1 at 77 K). Both narrow components, which have the same decay, form a dual phosphorescence of the long-wavelength form of this compound, which is caused by efficient thermal exchange between T ₁ and T ₂ levels in the course of deactivation to the ground state.     

An explanation of the very low fluorescence and phosphorescence in pyridine: a CASSCF/CASMP2 study

In this work, we applied the multiconfigurational complete active space self-consistent field method and the multiconfigurational second-order perturbation theory CASMP2 to study the fundamental excited states of pyridine and its possible photophysical and photochemical transformations. Our calculations, which are in agreement with the experimental results corresponding to excitations around the 0–0 transition, showed that the very low experimentally observed fluorescence of pyridine is due to the presence of two almost isoenergetic crossings, one of triple character, S₁/T₁/S₀ and the other of S₁/S₀ character. Both crossings are below the minimum of S₁(nπ^*) and have a common transition state (S₁(TS)) with a very low energy barrier (1.85 kcal/mol or 0.08 eV at the CASMP2 level of theory) separating them. A third triple crossing of the type S₁/T₁/S₀ lying lower with respect to the other two elucidates the observed T₁→S₀ radiationless transition. This explains not only pyridine's very low fluorescence and phosphorescence but also its almost negligible photochemistry, showing that photophysics is the prevalent process in this molecule.     

Anomalous (S2 → S0) luminescence of some derivatives of triphenylmethane dyes and their complexes with rare earth metals

Anomalous S₂ → S₀ fluorescence and T₂ → S₀ phosphorescence have been found in several triphenylmethane derivatives. This phenomenon can be explained by a large energy gap between the S₂ and S₁ levels, approximately 14000 cm^?1. Some of the investigated compounds exhibit also a normal long-wave fluorescence in spite of the fact, that the S₂ ? S₁ energy gap does not change significantly. However, in these cases absorption spectra reveal a high oscillator strength of the S₁ → S₀ transition. The coordination of a lanthanide ion quenches in several cases the normal S₁ → S₀ fluorescence whereas the S₂ → S₀ one is not affected significantly.     

Formation of intersystem crossing transitions in Pd(II) and Pt(II) porphyrins: Nonplanar distortions of the macrocycle and charge transfer states

We found new bands in the absorption spectra of Pt(II) and Pd(II) complexes of octaethylporphyrin and tetraphenylporphyrin that differ in the nature, number, and position of their side substituents. The bands are observed at 295 K in the range 570–690 nm and are attributed to spin-forbidden transitions from the ground S ₀ state to the excited T ₁ and T ₂ triplet states (the internal heavy atom effect). We determined the frequency distribution, number, and nature of these transitions, as well as their extinction coefficients (? = 6.0–210.0 M^?1 cm^?1), using computer decomposition of complex contours into Gaussian components and additional data obtained from the phosphorescence and phosphorescence excitation spectra of these complexes (295–77 K). In comparison to Pd complexes of porphyrins with planar macrocycles, nonplanar distortions of the tetrapyrrole macrocycle in the ground S ₀ state of the sterically hindered PdOETPP molecule cause a bathochromic shift of the bands of the electronic spin-forbidden S ₀ → T ₁ and S ₀ → T ₂ transitions, as well as an increase in their extinction coefficients. For the PdOEP-Ph(o-NO₂) molecule, which contains the electron acceptor nitro group, an absorption band attributed to an electronic transition from the ground state S ₀ to a charge transfer state (λ_max = 905 nm, ? = 10.0 M^?1 cm^?1) is observed at 295 K.     

The Phosphorescence Excitation Spectrum of Jet-Cooled Xanthione in the Region of the T1←S0 and S1←S0 Absorption Transitions

The ³A₂(nπ*)→¹A₁X (T₁→S₀) phosphorescence excitation spectrum of jet-cooled xanthione was investigated in the region 14 920-17 600 cm⁻¹. The structure observed is shown to be due to the T₁←S₀ absorption and an assignment in terms of the vibronic structure of that band is proposed. A previous assignment of the S₁←S₀ origin is considered in detail and the transition involved is shown to be most probably due to absorption of a vibronic triplet state T_1z,ν7. An alternative but tentative assignment of the S_1,0←S_0,0 transition is suggested. Comparison is made with previous spectroscopic and theoretical work on the molecule and its congeners, 4H-pyran-4-thione and 4H-1-benzopyran-4-thione.     

Fine-structure phosphorescence and radiative deactivation of the lowest triplet states in the most toxic dioxins

The transition dipole moments for the transition T₁(ππ*) → S₀ to vibrational energy levels of the nontotally symmetric vibrational modes of 2,3,7,8-tetrachloro-and 1,2,3,7,8-pentachlorodibenzo-p-dioxins are calculated. The interpretation of the fine-structure phosphorescence spectrum of the first of these compounds is refined, and the radiative deactivation rate constants for the s sublevels of the lowest triplet state T₁ are estimated. For a number of polychlorinated compounds, the effect of chlorine atoms occupying the α and β positions in a molecule on the T^s → S₀ transition dipole moments is discussed.     

Phosphorescence decay times of thiocyanate complexes of chromium (III) in DMSO

We report the phosphorescence spectra and decay times of chromium (III) solvo-complexes of the [Cr(NCS)_6?n(DMSO)_n]^n?3 type. It is shown that the decay times are linked with the number of solvated molecules. The rate of phosphorescence decay of mixed solvo-complexes depends mainly on the maximum vibrational frequency and number of coordinated molecules.     

Photophysical Processes in the Gas Phase at High Levels of Vibrational Excitation of Triplet Molecules of Benzophenone and Fluorenone

By the delayed fluorescence activated by direct multiphoton excitation of triplet molecules by CO₂–laser radiation we have studied the prevailing deactivation pathways of triplet molecules with a high store of vibrational energy E _vib. The dependences of the kinetic characteristics of delayed fluorescence on the presence of vapors and foreign gases have been used to estimate the rates and efficiencies of intermolecular vibrational relaxation in the vibrational quasi–continuum of the triplet state T ₁. By the changes in the intensities and decay rates over a wide range of vibrational energies we have established the E _vib dependences of reversible intercombination conversion between the states T ₁ and S ₁ and interconversion from T ₁ to the ground electronic state S ₀ for both the case of isolated excited molecules and at a steady vibrational temperature. It is shown that at high vibrational temperatures the radiationless transition from the T ₁ state to S ₀ has an activation character and is accomplished through the energy barrier. The conditions for going to an exponential dependence have been determined. It has been found that the obtained dependences are in good agreement with the known experimental results. The influence of molecular and environmental characteristics on the decay rate of triplet molecules is compared.