Joint experimental and theoretical study of spectral-luminescent properties and electronic structure of the molecules of new phthalocyanine analogues -derivatives of octaphenylporphyrazine and tetrakis (tert-butyl)
Spectral and luminescent properties of a new phthalocyanine analog, the magnesium complex of diphenyl substituted mono (1,4-diazepino)tribenzoporphyrazine, have been studied at 293 and 77 K. The results have been explained on the basis of quantum-chemical calculations for both this molecule and its simpler analogs with respect to 6H/1H-isomerism of the 1,4-diazepine ring. The small difference between the ground-state energies for the 6H and 1H isomers makes tautomerism between them possible. It is shown that the electronic transitions with intramolecular charge transfer from the diazepine fragment to the macrocycle have relatively low energy, especially for the 1H isomers. These states can be of considerable importance for photophysical and photochemical processes. A comparison of the theoretical and experimental electronic absorption spectra has confirmed that the diazepine ring in the substituted Mg-diazepinoporphyrazine is present in the 6H-form. It is established that substitution of one benzene ring by a diazepine fragment leads to quenching of fluorescence, decreasing its quantum yield to 27% (for Mg-phthalocyanine 76%).Introduction. The synthesis and investigation of phthalocyanine analogs, including those with rings other than benzene, are currently of great interest in the chemistry of porphyrins and phthalocyanines. Such compounds are expected to possess fundamentally different physicochemical properties and to be promising for creating new materials with given properties.Octaphenyl derivatives of porphyrazine (tetraazaporphine) with four annelated 7-membered diazepine rings, both the free bases and the metal complexes, have been synthesized and characterized [1,2]. We use for these the abbreviations MPADz 4 Ph 8 (M = 2H, Mg, Zn), where PA is porphyrazine; Dz, diazepine; and Ph, phenyl.
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