Zintl ions composed of Group 13, 14, and 15 elements are multiply charged cluster anions that form the building blocks of the Zintl phase. Superalkalis, on the other hand, are cationic clusters that mimic the chemistry of the alkali atoms. It is, therefore, counterintuitive to expect that Zintl anions can be used as a core to construct superalkalis. In this paper, using density functional theory, we show that this is indeed possible. The results are compared with calculations at the MP2 level of theory. A systematic study of a P7(3-) Zintl core decorated with organic ligands [R = Me, CH2Me, CH(Me)2 and C(Me)3] shows that the ionization energies of some of the P7R4 species are smaller than those of the alkali atoms and hence can be classified as superalkalis. This opens the door to the design and synthesis of a new class of superalkali moieties apart from the traditional ones composed of only inorganic elements.

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Superalkalis are complexes that have a lower ionization energy than that of the corresponding alkali and alkaline earth metals. Based on First Principles calculations, the plausible existence of a superalkali complex consisting of an all-metal aromatic trigonal Au3 core coupled with pyridine (Py) and imidazole (IMD) ligands is suggested. The calculated ionization energy (IE) values of the subsequent organometallic complexes, Au3(Py)3 and Au3(IMD)3, are low, thereby mimicking the usual behavior of a superalkali. First order hyperpolarizability calculations show the existence of non-linear optical properties in some of the complexes, which is also on par with the properties of a superalkali.

Execution of compositional doping by more than one element simultaneously inside carbon matrix is a challenging task for designing advanced carbon-based materials and nanotechnology. Herein, we have integrated a template-free...

The assembly of atoms leads to the formation of clusters. These clusters have a tendency to gain their stability by forming either cations or anions. Among the anionic clusters, Zintl ions with multiple negative charges are a special type of inorganic complex generally formed from group 13, 14 and 15 elements in the periodic table. On the other hand, superhalogens are neutral molecules which have high electron affinity. Between the two different types of molecules, the former stabilized in the neutral state by forming a phase with alkali metal atoms, while the latter prefers the anionic state. Using first principle calculations, we show that it is also possible to design superhalogens having a Zintl core by functionalizing with suitable ligands like CF, CN and NO. The vertical detachment energies of these complexes indicate that they can be classified as superhalogens. The stability of these complexes is explained in terms of the jellium model. Density of states, partial density of states and natural localized molecular orbitals (NLMO) of these molecules lend additional information on the structure and bonding of these complexes.