Experimental Evidences on Magnetism-Covalent Bonding Interplay in Structural Properties of Solids and during Chemisorption

Valence electrons are one of the main players in solid catalysts and in catalytic reactions, since they are involved in several correlated phenomena like chemical bonding, magnetism, chemisorption, and bond activation. This is particularly true in the case of solid catalysts containing d-transition metals, which exhibit a wide range of magnetic phenomena, from paramagnetism to collective behaviour. Indeed, the electrons of the outer d-shells are, on one hand, involved in the formation of bonds within the structure of a catalyst and on its surface, and, on the other, they are accountable for the magnetic properties of the material. For this reason, the relationship between magnetism and heterogeneous catalysis has been a source of great interest since the mid-20th century. The subject has gained a lot of attention in the last decade, thanks to the orbital engineering of quantum spin-exchange interactions and to the widespread application of external magnetic fields as boosting tools in several catalytic reactions. The topic is discussed here through experimental examples and evidences of the interplay between magnetism and covalent bonding in the structure of solids and during the chemisorption process. Covalent bonding is discussed since it represents one of the strongest contributions to bonds encountered in materials.