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The photo-oxidative stability of various annelated and substituted tetraazaporphyrin derivatives were investigated in N,N-dimethylformamide by irradiation in the presence of air. First-order rate constants were calculated. In addition, the positions of the HOMO and LUMO energy levels of the compounds were calculated using a commercially available program. A linear correlation between the experimental values of the rate constants and the theoretical values of the HOMO position exists. The method described allows one to predict the photo-oxidative stability by calculating their HOMO levels, which is very important for the use of macrocyclic metal complexes in photo-oxidation reactions in solution. From the calculated triplet energies it is considered that the macrocyclic metal complexes can convert by photoinduced energy transfer triplet oxygen to singlet oxygen. Experimentally, tetraazaporphyrin derivatives show high quantum yields of singlet oxygen formation under irradiation. No correlations of the quantum yields with the position of the HOMOs or with the rate constants of decomposition was observed.

The columnar mesomorphism of triphenylene-, phthalocyanine-, tetraazaporphyrin- and porphyrin-based compounds is briefly reviewed and the potential use of this particular supramolecular structure for charge-conducting devices is discussed. Suitably substituted triphenylenes exhibit ideal material properties for photoconducting devices, and well-aligned layers have been shown to give a very high charge carrier mobility of 0.1 × 10^-4m²V^-1s^-1 (time-of-flight measurements). From a molecular point of view, porphyrin systems should be superior to triphenylenes, but the properties of their mesophases do not support the advantageous homeotropic alignment of the columnar stacks. However, pulse radiolysis time-resolved microwave conductivity measurements revealed the highest charge carrier mobility value of 0.28 × 10^-4m²V^-1s^-1 for mesomorphic phthalocyanines.

The preparation and optical properties of peripherally substituted phthalocyanines and their analogs (i.e. naphthalocyanines, anthracyanines, aza-analogs of phthalocyanines, and tetraazaporphyrins) have been widely discussed. This review highlights methodologies that have been published in poorly known and mostly unavailable Russian journals.

Various asymmetrically substituted phthalocyanines (Pcs) and porphyrazines (Pzs) have been synthesized in good yields using a solid-phase synthesis method with a poly(ethylene glycol) (PEG) resin attached to an indole linker as the solid support. These compounds are formed by cross condensation of maleonitrile or phthalonitrile with another phthalonitrile covalently bonded to the solid support with an amino linking group. The polymer bound Pc or Pz is separated by filtration, and washing the symmetrical Pc or Pz by-product. The amine Pc-appended to polyethylene glycol resin is further reacted to yield azide whilst still on the solid support. Cleavage of the Pc or Pz off the solid support results in 3:1 asymmetric Pz or Pz with high degree of purity, requiring minimal further purification. The use of hydrophilic PEG-based resin allows the symmetrical compound to be removed completely by washing whereas the acid labile indole linker makes it easier to cleave the product under mild conditions. The conjugation abilities of these compounds have been demonstrated by the successful conjugation of one of the azide Pcs with a peptide elaborated with an alkyne function. Use of microwave for the synthesis of these compounds results in shorter reaction times, higher yields and higher degree of purity.

In 2005, Kobayashi and coworkers reported trends in the TD-DFT spectra of 17 Zn(II) porphyrinoids [J. Am. Chem. Soc. 2005; 127: 17697] that were analyzed using Michl's perimeter model as part of a study of the anomalous magnetic circular dichroism (MCD) spectroscopy of zinc tetraphenyltetraacenaphthoporphyrin. In recent years, it has become increasingly clear that TD-DFT calculations with the commonly used hybrid B3LYP exchange-correlation functional of the Gaussian software package are problematic in the B-band region of porphyrinoid spectra, since the degree of configurational interaction between the B and higher energy ππ* state appears to be significantly overestimated. The CAM-B3LYP functional is now often preferred for analyzing the optical properties of porphyrinoids, since it includes a long-range correction of the exchange potential, which incorporates an increasing fraction of Hartree–Fock (HF) exchange as the interelectronic separation increases, making it better suited for studying compounds where there is significant charge transfer in the electronic excited states. The trends in the TD-DFT calculations are reexamined with a wider range porphyrinoid compounds including several with pyrazino moieties and are found to provide a closer agreement with the experimental in the B-band region for complexes such as zinc tetraphenylporphyrin and phthalocyanine.