Phosphorene, the 2D material derived from black phosphorus, has recently attracted a lot of interest for its properties, suitable for applications in materials science. The physical features and the prominent chemical reactivity on its surface render this nanolayered substrate particularly promising for electrical and optoelectronic applications. In addition, being a new potential ligand for metals, it opens the way for a new role of the inorganic chemistry in the 2D world, with special reference to the field of catalysis. The aim of this review is to summarize the state of the art in this subject and to present our most recent results in the preparation, functionalization, and use of phosphorene and its decorated derivatives. We discuss several key points, which are currently under investigation: the synthesis, the characterization by theoretical calculations, the high pressure behavior of black phosphorus, as well as its decoration with nanoparticles and encapsulation in polymers. Finally, device fabrication and electrical transport measurements are overviewed on the basis of recent literature and the new results collected in our laboratories.

We studied the chemical-physics and the nature of the interactions involved in the formation of adducts of two-dimensional black phosphorus (2D BP) with organoboron derivatives of a conjugated fluorescent molecule (pyrene). Time-resolved fluorescence spectroscopy showed a stabilization effect of 2D BP on all the organoboron derivatives, in particular for the adducts endowed with the boronic functionalities. Also, a stronger modulation of the fluorescence decay with oxygen was registered for one of the adducts compared to the corresponding organoboron derivative alone. NMR experiments in suspension and DFT simulations confirmed that only non-covalent interactions are involved in the formation of the adducts. The energetic gain in their formation arises from the interaction of P atoms with both C atoms of the pyrene core and with B atom of the boronic functionalities, with a stronger contribution from the ester with respect to the acid one. The interaction results in a lowering of the band gap of 2D BP by around 0.10 eV. Furthermore, we demonstrated through Raman spectroscopy an increased stability towards oxidation in air of 2D BP in the adducts in the solid state (more than six months). The modification of the electronic structure at the interface between 2D BP and a conjugated organic molecule through non-covalent stabilizing interactions mediated by the B atom is particularly appealing in view of creating heterojunctions for optoelectronic, photonic and chemical sensing applications.