Many complex mechanisms underlying the fascinating functionalities provided by tetrapyrrolic macrocycles in biochemistry have been already unraveled. Light harvesting, molecular transport, and catalytic conversion are some of the processes performed by tetrapyrrole-based centers embedded in protein pockets. The main function is determined by the single atom species that is caged in the macrocycle, while a finer tuning (band gap, chemical selectivity etc) is granted by the geometric and electronic structure of the tetrapyrrole, including its residues, and by the proximal and distal structures of the protein surroundings that exploit the molecular trans-effect and direct weak interactions, respectively. Hence, a scientific and technological challenge consists in the artificial replication of both structure and functionality of natural reaction centers in 2D ordered arrays at surfaces. Nano-architected 2D metalorganic frameworks can be indeed self-assembled under controlled conditions at supporting surfaces and, in the specific, porphyrin- and phthalocyaninebased systems have been widely investigated in ultra-high vacuum conditions by means of surface science approaches. Deep insight into the geometry, electronic structure, magnetic properties, ligand adsorption mechanisms, and light absorption has been obtained, with the strong experimental constraint of vacuum. Especially in the case of the interaction of tetrapyrroles with ligands, this limit represents a relevant gap with respect to both comparison with natural counterparts from the liquid environment and potential applicative views at both solid–liquid and solid–gas interfaces. Thus, a step forward in the direction of near-ambient pressure is strongly necessary, while maintaining the atomiclevel detail characterization accuracy. Nowadays this becomes feasible by exploiting state-of-the-art experimental techniques, in combination with computational simulations. This review focusses on the latest advances in this direction.
