Synthesis of mono-, di-, tri- and tetracarboxy azaphthalocyanines as potential dark quenchers

Abstract Mono-, di-, tri- and tetracarboxy-substituted metal-free azaphthalocyanines (AzaPc) were synthesized from 5,6-bis(diethylamino)pyrazine-2,3-dicarbonitrile and 6-(5,6-dicyano-3-(diethylamino)pyrazin-2-ylamino)hexanoic acid using a statistical condensation approach. AzaPc bearing eight diethylamino peripheral substituents was also isolated from the mixture. Analysis of the distribution of congeners in the statistical mixture using optimized HPLC method (Phenomenex Synergy RP Fusion column, acetonitrile/tetrahydrofuran/water (pH 5.5) 50:20:30) was performed. The analysis showed optimal ratios of starting materials to be 3:1 for AAAB, 1:3 for ABBB and 1:1 for AABB/ABAB types of the congeners. The distribution of the congeners corresponded well with calculated values indicating similar reactivity of both starting materials and no sterical constraint between adjacent isoindole units in the AzaPc ring. All investigated AzaPc showed no fluorescence, extremely low singlet oxygen quantum yields ( Φ ∆