Energy transfer in chemical dimers of porphyrins and chlorins by the methods of selective laser spectroscopy at 1.8–10 K

The methods of selective laser spectroscopy applied at 1.8–10 K to a glass-forming tetrahydrofuran-toluene (3∶1) mixture have revealed that in the dimers of tetrapyrrole compounds (ethane-bis-octaethylporphyrins, ethane-bis-Zn-octaethylchlorins, heterodimers of Zn-cyclopentane porphyrins) the exciton interactions (V₁₂≈118 cm⁻¹) and S-S-transfer of energy (of probability F≈11 sec⁻¹) are implemented under conditions of substantial inhomogeneous broadening (δF_1/2≈50 cm⁻¹). Upon excitation of a donor component in the dimers, one observes a strong quenching of its emission, the disappearance of the fine structure in the fluorescence spectra, a decrease in the efficiency of spectral hole burning by, approximately, an order of magnitude, and a 12-fold increase in their halfwidth. To whom correspondence should be addressed. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 500–504, July–August, 1999.     

Anticrossing of triplet exciton levels in persistence spectra of GaSe crystal

The effect of spin sublevel anticrossing in the persistence spectra of triplet excitons was investigated. The anticrossing signal shape was found to change substantially during the excited-state lifetime. The anticrossing signal splits into two peaks, with the separation between them increasing with time. It is shown that each of the peaks is caused by the contribution of one of the interacting states to the emission, and their lifetimes are determined.     

Fractals of graphene quantum dots in photoluminescence of shungite

Viewing shungite as loosely packed fractal nets of graphene-based (reduced graphene oxide, rGO) quantum dots (GQDs), we consider photoluminescence of the latter as a convincing proof of the structural concept as well as of the GQD attribution to individual rGO fragments. We study emission from shungite GQDs for colloidal dispersions in water, carbon tetrachloride, and toluene at both room and low temperatures. As expected, the photoluminescence of the GQD aqueous dispersions is quite similar to that of synthetic GQDs of the rGO origin. The morphological study of shungite dispersions shows a steady trend of GQDs to form fractals and to drastically change the colloid fractal structure caused by the solvent exchange. Spectral study reveals a dual character of the emitting centers: individual GQDs are responsible for the spectra position while the fractal structure of GQD colloids ensures high broadening of the spectra due to structural inhomogeneity, thus causing a peculiar dependence of the photoluminescence spectra on the excitation wavelength. For the first time, photoluminescence spectra of individual GQDs were observed in frozen toluene dispersions, which paves the way for a theoretical treatment of the GQD photonics.     

Halide ion determination from luminescence of the diprotonated form of porphyrin

We have studied quenching of the fluorescence of the diprotonated form of 3,7,13,17-tetramethyl-2,8,12,18-tetrabutylporphyrin by iodide ions in solutions. We have established that there is both static quenching of fluorescence when nonfluorescent complexes are formed with the iodide ions, as a result of an internal heavy atom effect, and also dynamic diffusion-controlled quenching. Based on analysis of the dependences of the fluorescence intensity and fluorescence lifetime on the iodide ion concentration in solution, we suggest using the diprotonated form of this porphyrin as the base compound for designing a fluorescent molecular receptor for halide ions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 750–755, November–December, 2007.     

Influence of spin-orbit coupling on vibronic spectra of metalocomplexes porphin: Manifestation of out-of-plane vibrations

In fine-structure phosphorescence spectra of metallocomplexes of porphin with ions of the Pd(II) and Pt(II) and their meso-deuterated derivatives additional lines have been detected which have no analogs in fluorescence and resonance Raman spectra of metalloporphyrins and in phosphorescence spectra of metallocomplexes of porphin with light ions of the Mg(II) and Zn(II). For Zn-porphin, quantum-chemical calculations of frequencies and forms of in-plane and out-of-plane vibrations have been performed. Based on experimental data and calculation results it has been found, that in vibronic phosphorescence spectra of metallocomplexes of porphin, out-of-plane gerade modes of the E _g symmetry (D _4h symmetry group) are manifested. The activity of out-of-plane vibrations increases with enhancing spin-orbital coupling upon changing to heavier chelated metal ions. Vibronic transitions with participation of out-of-plane gerade E _g vibrations manifest in the T ₁ → S ₀ transition through the vibronic intensity borrowing from the triplet-triplet ³ E _u -³ E _g transition.     

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.