MTHPP monoacetic ester: unexpected formation, zinc metalation, thermal and photophysical properties

Abstract

AbstractIn the current investigation we report an unexpected methyl esterification occurred during the coupling reaction of mTHPP monoacetic acid 2 with 3-amino-1,2,4-triazole in the presence of HBTU/DIPEA. The mechanism of this unexpected methyl esterification was studied, and the structure of the formed methyl ester 5 was confirmed by the means of 1H, 13C NMR in addition to (MALDI-TOF and ESI-HRMS) spectrometry. The formation of 5 during the coupling reaction was also chemically supported by an alternative synthetic method involving a direct monosubstitution reaction of mTHPP 1 with methyl bromoacetate. We also investigated the metalation of 5 with zinc and studied the thermal properties along with differential scanning calorimetry (DSC) of the zinc porphyrin 6. The photophysical properties of porphyrin methyl ester 5 and its zinc complex 6 were also investigated. Graphical Abstract