Following the introduction of an efficient method for the preparation of technetium-99m complexes containing a terminal Tc-N multiple bond, under conditions suitable for nuclear medicine applications, new radiopharmaceuticals for heart and brain imaging have been discovered. These compounds belong to the class of bi-substituted, square-pyramidal nitride TcV complexes with dithiocarbamate ligands, and are the first examples of radiopharmaceuticals of this type exhibiting interesting biological properties. The peculiar chemical characteristics of the Tc-N core can also be conveniently utilized for the design of radiopharmaceuticals incorporating bioactive peptides and having definite structural features.