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The luminescent and photophysical properties of the etioporphyrin-I complex with indium(III) chloride, InCl-EtioP-I were experimentally studied at room and liquid nitrogen temperatures in pure and mixed toluene solutions. At 77 K, in a 1:2 mixture of toluene with diethyl ether, the quantum yield of phosphorescence reaches 10.2%, while the duration of phosphorescence is 17 ms. At these conditions, the ratio of phosphorescence-to-fluorescence integral intensities is equal to 26.1, which is the highest for complexes of this type. At 298 K, the quantum yield of the singlet oxygen generation is maximal in pure toluene (81%). Quantum-chemical calculations of absorption and fluorescence spectra at temperatures of 77 K and 298 K qualitatively coincide with the experimental data. The InCl-EtioP-I compound will further be used as a photoresponsive material in thin-film optoelectronic devices.

Stable subphthalocyanine-type dyes with a high electron affinity attract much attention as potential substitutes for traditional fullerenes in molecular electronics devices. One possible way to enhance the acceptor properties of the subphthalocyanine core is by replacing the peripheral benzene fragments (C6H4) with 1,2,5-thiadiazole fragments (C2N2S1). However, the resistance of these materials to light or atmospheric effect remains an open question, which limits their further application in device manufacturing. In this work, we compare vacuum-deposited films of three derivatives, SubPzS3H0 (all peripheral fragments are 1,2,5-thiadiazoles), SubPzS2H4 (two fragments are 1,2,5-thiadiazoles and one fragment is benzene), and SubPcS0H12 (all benzenes, i.e., parent subphthalocyanine). Practically relevant substrates were used for deposition, namely, bare glass, glass/ITO or FTO, and PET/ITO. Photobleaching of films under continuous 1 sun illumination was studied in laboratory air, synthetic air, and ultrapure argon. It is shown that the exclusion of near-UV photons from the incident light spectrum, which corresponds to the absorption of subphthalocyanines in the Soret-band, strongly inhibits degradation. Absorption in the Q-band range initiates soft annealing rather than photobleaching of films. The stability of the films deposited on glass decreases as SubPzS3H0 > SubPzS2H4 > SubPcS0H12 in air, and vice versa in argon. The substrate adds more complexity to this picture. In argon, the ITO coating reduces degradation of all of the compounds equally, in contrast to the glass samples, while in air, the SubPzS3H0 films discolor completely. The latter reaction proceeds due to the indium-containing species migrating from the conductive coating.

Electronic and geometric structures of metal-free, Al, Ga and In complexes with tetrapyrazinoporphyrazine (TPyzPA) and octachlorotetrapyrazinoporphyrazine (TPyzPACl8) were investigated by density functional theory (DFT) calculations and compared in order to study the effect of chlorination on the structure and properties of these macrocycles. The nature of the bonds between metal atoms and nitrogen atoms was described using the NBO-analysis. Simulation and interpretation of electronic spectra were performed with the use of time-dependent density functional theory (TDDFT). A description of calculated IR spectra was carried out based on the analysis of the distribution of the potential energy of normal vibrational coordinates.

The electronic and molecular structures of metal-free tetrabenzoporphyrin (H2TBP) and its complexes with zinc, cadmium, aluminum, gallium and indium were investigated by density functional theory (DFT) calculations with a def2-TZVP basis set. A geometrical structure of ZnTBP and CdTBP was found to possess D4h symmetry; AlClTBP, GaClTBP and InClTBP were non-planar complexes with C4v symmetry. The molecular structure of H2TBP belonged to the point symmetry group of D2h. According to the results of the natural bond orbital (NBO) analysis, the M-N bonds had a substantial ionic character in the cases of the Zn(II) and Cd(II) complexes, with a noticeably increased covalent contribution for Al(III), Ga(III) and In(III) complexes with an axial –Cl ligand. The lowest excited states were computed with the use of time-dependent density functional theory (TDDFT) calculations. The model electronic absorption spectra indicated a weak influence of the nature of the metal on the Q-band position.

The basic macrocyclic octapyridinotetrapyrazinoporphyrazine InIII complex of formula [Py8TPyzPzIn(OAc)]·8H2O, prepared by reaction of the free ligand [Py8TPyzPzH2]·2H2O with In(OAc)3, is a stable-to-air species of which the structure has been studied by its X-ray powder diffraction and mass spectra and characterization operated by IR and UV-visible spectral behavior. The complex has been further examined and proven to be of potential interest for its response as an anticancer agent in the field of photodynamic therapy (PDT), the value of ΦΔ = 0.55 (in DMF) being in the range of 0.4–0.6 at the level of similar phthalocyanine and porphyrazine analogs and qualifying the species as a highly efficient anticancer agent. Planned parallel types of investigation, including their photoactive behaviour in PDT, have been extended to the mononuclear octacation [(2-Mepy)8TPyzPzIn(OAc)]8+ (salted by iodide ions) and the heteropentanuclear derivatives [(M’Cl2)4Py8TPyzPzIn(OAc)]·xH2O (M’ = PdII, x = 8; PtII, x = 1)) and [{(Pd(CBT)2)4}Py8TPyzPzIn(OAc)]·19H2O (CBT = m-carborane-1-thiolate anion).