Zintl phases that contain molecule-like polyanions will often separate into its constituent anions and cations in liquid ammonia, ethylenediamene, crown ethers, or cryptand solutions. Therefore, they are referred to as Zintl ions.  The term clusters is also used to emphasize them as groups with homonuclear bonding. The structures can be described by Wade's rules and occupy an area of transition between localized covalent bonds and delocalized skeletal bonding. Beyond the "aesthetic simplicity and beauty of their structures" and distinctive electronic properties, Zintl ions are also of interest in synthesis because of their unique and unpredictable behavior in solution.
The largest subcategory of Zintl ions is homoatomic clusters of group 14 or 15 elements. Some examples are listed below.
Many examples similarly exist for heteroatomic clusters where the polyanion is composed of greater than one main group element. Some examples are listed below. Zintl ions are also capable of reacting with ligands and transition metals, and further 'heteroatomic examples are discussed below (intermetalloid clusters). In some solvents, atoms exchange can occur between heteroatomic clusters. Additionally, it is notable that fewer large cluster examples exist.