Abstract

Given the fundamental role of (metallo)porphyrins in various natural processes, integration of these functional units into artificial ensembles is an enduring task for supramolecular chemists.1a,b In this wide context, the metal-mediated assembling approach has afforded a variety of spectacular 3D discrete arrays of porphyrins with new functions, ranging from molecular recognition to (photo)catalysis.1c Over the years we also have employed (metallo)porphyrins and coordination compounds for the obtainment of discrete multi-component systems, mostly for artificial photosynthesis purposes.2 More recently, we expanded our interests towards two main directions: i. preparation and photophysical investigation of metalloporphyrins as photosensitizers/catalysts for H2 generation3a or as photoactive units to model Proton Coupled Electron Transfer processes;3b,c ii. possible strategies for the obtainment of heretoleptic porphyrin metallacycles.4 An excursion on the most fascinating past and recent examples will be presented. References 1. a) C.M. Drain, A. Varotto, I. Radivojevic, Chem. Rev. 2009, 109, 1630; b) S. Durot, J. Taesch, V. Heitz, Chem. Rev. 2014, 114, 8542; c) E.G. Percástegui, V. Jancik, Coord. Chem. Rev. 2020, 407, 213165. 2. a) M. Marchini, A. Luisa, G. Bergamini, N. Armaroli, B. Ventura, M. Baroncini, N. Demitri, E. Iengo, P. Ceroni, Chem. Eur. J. 2021, 27, 1625; b) A. Amati, G. Cecot, I. Regeni, E. Giraldi, N. Demitri, K. Severin, E. Iengo, manuscript in preparation. 3. a) refs in: K. Ladomenou, M. Natali, E. Iengo, G. Charalampidis, F. Scandola, A. G. Coutsolelos, Coord. Chem. Rev. 2015, 304-305, 38; b) M. Natali, A. Amati, N. Demitri, E. Iengo, Chem. Commun. 2018, 54, 6148; c) M. Natali, A. Amati, N. Demitri, E. Iengo, Chem. Eur. J. 2021, 27, 7872. 4. a) A. Vidal, F. Battistin, G. Balducci, E. Iengo, E. Alessio, Inorg. Chem. 2021, 60, 11503; b) A. Vidal, D. Rossato, E. Iengo, G. Balducci, E. Alessio, Chem. Eur. J. 2023, doi.org/10.1002/chem.202300893; c) S. Simonato, C. Mucignato, G. Fogar, E. Zangrando, G. Balducci, E. Iengo, unpublished results.