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We demonstrate that the action of physical pressure, chemical compression, or aliovalent substitution in ACo2As2 (A = Eu and Ca) has a general consequence of causing these antiferromagnetic materials to become ferromagnets. In all cases, the mixed valence triggered at the electropositive A site results in the increase of the Co 3d density of states at the Fermi level. Remarkably, the dramatic alteration of magnetic behavior results from the very minor (0.15 electron) change in the population of the 3d orbitals. The mixed valence state of Eu observed in the high-pressure (HP) form of EuCo2As2 exhibits a remarkable stability, achieving the average oxidation state of +2.25 at 12.6 GPa. In the case of CaCo2As2, substituting even 10% of Eu or La into the Ca site causes ferromagnetic ordering of Co moments. Similar to HP-EuCo2As2, the itinerant 3d ferromagnetism emerges from electronic doping into the Co layer because of chemical compression of Eu sites in Ca0.9Eu0.1Co1.91As2 or direct electron doping in Ca0.85La0.15Co1.89As2. The results reported herein demonstrate the general possibility of amplifying minor localized electronic effects to achieve major changes in material's properties via involvement of strongly correlated electrons.

AlFe2B2 was prepared by two alternative synthetic routes, arc melting and synthesis from Ga flux. In the layered crystal structure, infinite chains of B atoms are connected by Fe atoms into two-dimensional [Fe2B2] slabs that alternate with layers of Al atoms. As expected from the theoretical analysis of electronic band structure, the compound exhibits itinerant ferromagnetism, with the ordering temperature of 307 K. The measurement of magnetocaloric effect (MCE) as a function of applied magnetic field reveals isothermal entropy changes of 4.1 J kg(-1) K(-1) at 2 T and 7.7 J kg(-1) K(-1) at 5 T. These are the largest values observed near room temperature for any metal boride and for any magnetic material of the vast 122 family of layered structures. Importantly, AlFe2B2 represents a rare case of a lightweight material prepared from earth-abundant, benign reactants which exhibits a substantial MCE while not containing any rare-earth elements.