A trans-ortho asymmetrically di-strapped metalloporphyrin integrating three key structural features of ligand in heme

Heme responsible for the dioxygen fixation, transport and conversion is a metalloporphyrin complex highly dependent on its diverse geometry of ligand. In this work, a trans-ortho-di-strapped zinc porphyrin with dome-like deformation was synthesized by thermodynamically controlling the formation of trans-precursor of porphyrinogen. Its single-crystal structure demonstrated that the asymmetric treatment of porphyrin achieves three goals of creating two secondary coordination sphere (SCS) bulks, maintaining a unique dome deformation, and making atomic out-of-plane deviation. In this way, this metallic complex integrates at least three key features of the pocket structure, the differentiated axial ligations, and the ring distortion, making it an ideal heme analog. An asymmetrically trans-ortho-di-strapped zinc porphyrin as heme mimic integrates its three key features of pocket structure, differentiated axial ligation, and ring distortion. [Display omitted]