Ricerc@Sapienza

Meso-tetraphenylporphyrin connected with a ferrocene molecule in the beta-position of the macrocycle through a triple carbon-carbon bond has been bound to carbon spheres using the Prato-Maggini reaction. The ethynyl or/and phenylene ethynylene subunits were chosen as a linking bridge to give a high conjugation degree between the donor (i. e., ferrocene), the photoactive compound (i. e., porphyrin), and the acceptor (i. e., carbon spheres).

A novel family of nanocarbon‐based materials were designed, synthesized, and probed within the context of charge‐transfer cascades. In details, we implemented fine‐tuned chains of photo‐ and redox‐active constituents. For the first time, we integrated electron‐donating ferrocenes with light‐harvesting /electron‐donating (metallo)porphyrins and electron‐accepting graphene nanoplates (GNP) into multicomponent conjugates. To control the rate of charge flow between the individual building blocks, we bridged them via oligo‐ p ‐phenyleneethynylenes of variable lengths.

The impressive chemistry shown by porphyrins in natural systems is particularly attractive for exploitation in chemical sensors. In these devices the sensing mechanisms can mimic most of the porphyrin biological reactivity, such as reversible binding, activation of small molecules, redox activity, and photoactivated processes. The simultaneous presence of multiple binding mechanisms allows porphyrins to interact with a large variety of analytes.

The binding energy of CO, O-2 and NO to isolated ferric heme, [(FeP)-P-III](+), was studied in the presence and absence of a sigma donor (N-methylimidazole and histidine) as the trans axial ligand. This study combines the experimental determination of binding enthalpies by equilibrium measurements in a low temperature ion trap using the van't Hoff equation and high level DFT calculations.