António Paulo

Due to their favorable chemical features, Re and Tc complexes have been widely used for the development of new therapeutic agents and imaging probes to solve problems of biomedical relevance. This review provides an update of the most relevant research efforts towards the development of novel cancer theranostic agents using Re and Tc‐based compounds interacting with specific DNA structures. This includes a variety of homometallic complexes, namely those containing M(CO) 3 (M=Re, Tc) moieties, that exhibit different modes of interaction with DNA, such as covalent binding, intercalation, groove binding or G‐quadruplex DNA binding. Additionally, heterometallic complexes, designed to potentiate synergistic effects of different metal centers to improve DNA‐targeting, cytotoxicity and fluorescence properties, are also reviewed. Particular attention is also given to 99m Tc‐ and 188 Re‐labeled oligonucleotides that have been widely explored to develop imaging and therapeutic radiopharmaceuticals through the in vivo hybridization with a specific complementary DNA or RNA target sequence to provide useful molecular tools in precision medicine for cancer diagnosis and treatment. Finally, the need for further improvement of DNA‐targeted Re and Tc‐based compounds as potential therapeutic and diagnostic agents is highlighted, and future directions are discussed.