Photochemical Behavior of Beryllium Complexes with Subporphyrazines and Subphthalocyanines

Structures of beryllium subphthalocyanines and beryllium subporphyrazines complexes with different substituents are explored for the first time. Their photochemical properties are studied using time-dependent density functional theory calculations and compared to boron-related compounds for which their photochemical activity is already known. These beryllium compounds were found to be thermodynamically stable in a vacuum and present features similar to those of boron-containing analogues, although the nature of bonding between the cation and the macrocycle presents subtle differences. Most important contributions to the main peak in the Q-band region arise from HOMO to LUMO transitions in the case of subphthalocyanines and alkyl subporphyrazine complexes, whereas a mixture of that contribution and a HOMO-2 to LUMO contribution are present in the case of thioalkyl subporphyrazines. The absorption in the visible region could make these candidates suitable for photochemical devices if combined with appropriate donor groups.