Review Perspectives of molecular and nanostructured systems with d- and f-block metals in photogeneration of reactive oxygen species for medical strategies Joanna Kuncewicz ⇑ , Janusz M. Da ˛ browski, Agnieszka Kyziol, Malgorzata Brindell, Przemyslaw Labuz, Olga Mazuryk, Wojciech Macyk, Gra _ zyna Stochel ⇑ Faculty of Chemistry, Jagiellonian University, ul. Gronostajowa 2, 30-387 Kraków, Poland article info Article history: Received 25 March 2019 Received in revised form 11 July 2019 Accepted 14 July 2019 Keywords: Reactive oxygen species Transition metals Lanthanides Metal complexes Semiconductors Nanomaterials Photosensitization Photocatalysis abstract The photogeneration of reactive oxygen species (ROS) by molecular and nanostructured systems with d- and f-metal compounds is discussed with the emphasis on the mechanisms involved in the process. The effectiveness of ROS photogeneration in various systems from simple metal complexes with non-macrocyclic and macrocyclic ligands, through more complex supramolecular scaffolds, up to nano-platforms and hybrid materials is reviewed considering their biological and medical applications. A particular emphasis is focused on the comparison of mechanisms of ROS photogeneration exploited in d- versus f-metal systems. Perspectives for each type of systems are also outlined. Ó 2019 Elsevier B.V. All rights reserved. Contents 1. Introduction ........................................................................................................... 2 2. Electronic structure vs. possible processes ................................................................................... 2 3. Reactive oxygen species.................................................................................................. 4 4. Photogeneration of ROS .................................................................................................. 6 4.1. Mechanisms of ROS photogeneration by molecular and nanoparticulate systems .............................................. 6 4.2. Metal complexes with non-macrocyclic ligands ......................................................................... 9 4.2.1. d-block metal complexes .................................................................................... 9 4.2.2. f-block metal complexes ................................................................................... 11 4.3. Macrocyclic complexes ............................................................................................ 12 4.3.1. d-block metal macrocyclic complexes ......................................................................... 12 4.3.2. f-block metal macrocyclic complexes ......................................................................... 13 4.4. Nanostructures .................................................................................................. 14 4.4.1. Nanostructures based on d-block metals ...................................................................... 14 4.4.2. Nanostructures based on f-block metals ....................................................................... 21 5. Conclusions and perspectives ............................................................................................ 27 Acknowledgement ..................................................................................................... 28 References ........................................................................................................... 28 https://doi.org/10.1016/j.ccr.2019.07.009 0010-8545/Ó 2019 Elsevier B.V. All rights reserved. ⇑ Corresponding authors. E-mail addresses: kuncewic@chemia.uj.edu.pl (J. Kuncewicz), stochel@chemia.uj.edu.pl (G. Stochel). Coordination Chemistry Reviews 398 (2019) 113012 Contents lists available at ScienceDirect Coordination Chemistry Reviews journal homepage: www.elsevier.com/locate/ccr