The contribution of metalloporphyrin complexes in molecular sensing and in sustainable polymerization processes: a new and unique perspective.

This review highlights the recent developments in the field of metalloporphyrins as optical probes for biologically relevant molecules, such as nitric oxide (NO) and hydrogen sulfide (H2S), and as catalysts for the preparation of sustainable polymers such as polyesters, by the ring-opening polymerization (ROP) of cyclic esters and the ring-opening co-polymerization (ROCOP) of epoxides and anhydrides, and polycarbonates by the chemical fixation of carbon dioxide (CO2). The great potential of porphyrins is mainly due to the possibility of making various synthetic modifications to the porphyrin ring, such as modifying the coordinated metal, peripheral substituents, or even the molecular skeleton. Due to the strict structure-property relationships, one can use porphyrinoids in several different applications such as, for instance, activation of molecular oxygen or catalysis of photosynthetic processes. These possibilities broaden the application of porphyrins in several different fields of research, further mimicking what nature does. In this context, here, we want to provide evidence for the great flexibility of metalloporphyrins by presenting an overview of results obtained by us and others in the research fields we are currently involved in. More specifically, we report a survey of our most significant achievements regarding their use as optical probes in the context of the results reported in the literature from other research groups, and of the use of porphyrin metal(iii) complexes as catalysts for sustainable polymerization processes. As for the optical probe section, in addition to the metalloporphyrins synthesized ad hoc in the laboratory, the present work also covers the natural proteins containing a porphyrin core.