Electronic structure and fluorescence of the Mg(II) complex of 1,4-diazepinotribenzoporphyrazine.

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 6 H/1 H-isomerism of the 1,4-diazepine ring. The small difference between the ground-state energies for the 6 H and 1 H 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 1 H 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 6 H-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%). [ABSTRACT FROM AUTHOR]