Pyrazinoporphyrazines and tribenzopyrazinoporphyrazines were synthesized and studied towards their potential applications in photodynamic therapy. The macrocycles were obtained via Linstead macrocyclization with good yields. The expansion of the porphyrazine periphery with hyperbranched aryl substituents was beneficial in terms of purification and isolation of compounds, effectively hampering their aggregation tendency in different concentrations. The obtained macrocycles were assessed for their singlet oxygen generation quantum yields and revealed far better efficacies for tribenzopyrazinoporphyrazines than pyrazinoporphyrazines. A comparison of the crystal packing of two 2,3-dicyanopyrazine derivatives revealed that the recurring motif of the supramolecular architecture is a dimer formed by π–π stacking interactions between aromatic pyrazine and phenyl rings of the inversion center related molecules.