A "Zintl Phase" was first observed in 1891 by M. Joannis, who noted an unexpected green colored solution after dissolving lead and sodium in liquid ammonia, indicating the formation of a new product. It was not until many years later, in 1930, that the stoichiometry of the new product was identified as NaPb by titrations performed by Zintl et al.; and it was not until 1970 that the structure was confirmed by crystallization with ethylenediamine (en) by Kummer.
In the intervening years and in the years since, many other reaction mixtures of metals were explored to provide a great number of examples of this type of system. There are hundreds of both compounds composed of group 14 elements and group 15 elements, plus dozens of others beyond those groups, all spanning a variety of different geometries. Corbett has contributed improvements to the crystallization of Zintl ions by demonstrating the use of chelating ligands, such as cryptands, as cation sequestering agents.
More recently, Zintl phase and ion reactivity in more complex systems, with organic ligands or transition metals, have been investigated, as well as their use in practical applications, such as for catalytic purposes or in materials science.