Sterically controlled and pH-dependent self-aggregation of synthetic zinc 3-(alkylamino)methylated chlorophyll-a derivatives in aqueous micellar solution

Abstract

Zinc methyl 3-(methyl/ethylamino)methyl-pyropheophorbides-[Formula: see text] were prepared as models of photosynthetically active bacteriochlorophyll-[Formula: see text] possessing the 3[Formula: see text]-hydroxy group. The synthetic methylamino analog predominantly dimerized via two Zn[Formula: see text]N coordination bonds in aqueous Triton X-100 micelles, while the more sterically crowding and less coordinating ethylamino derivative self-aggregated to form large oligomers through single coordination and hydrogen bonds, Zn[Formula: see text]N–H[Formula: see text]O=C-13, similarly as in the natural self-aggregates of bacteriochlorophyll-[Formula: see text]. The artificial self-aggregates were dependent on the aqueous pH, but the dimer was less pH-sensitive and also more tolerant to the additional Triton X-100.