Functionalized deltahedral Zintl complexes Ge₉R₃ (R = CF₃, CN, and NO₂): a new class of superhalogens

Abstract

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.

Can Superhalogen Ligand Make More Reactive Frustrated Lewis Pairs?

“…Keeping these options in mind, we have taken three different five membered heterocyclic ligands, viz., C 2 BNSHF 2 , C 2 BNSF 3 and C 2 BNO(CN) 3 with VDE values of 2.64 eV, 2.82 eV and 4.62 eV respectively. Among these ligands, C 2 BNO(CN) 3 can be assigned as superhalogen [51][52][53] due to its higher VDE than Cl. The optimized geometries of (C 2 BNSHF 2 ) 3 BÀ P( t Bu) 3 , Figure 1.…”

“…Keeping these options in mind, we have taken three different five membered heterocyclic ligands, viz., C 2 BNSHF 2 , C 2 BNSF 3 and C 2 BNO(CN) 3 with VDE values of 2.64 eV, 2.82 eV and 4.62 eV respectively. Among these ligands, C 2 BNO(CN) 3 can be assigned as superhalogen [51–53] due to its higher VDE than Cl. The optimized geometries of (C 2 BNSHF 2 ) 3 B−P( t Bu) 3 , (C 2 BNSF 3 ) 3 B−P( t Bu) 3 and [C 2 BNO(CN) 3 ] 3 B−P( t Bu) 3 along with some important bond distances, formal charges on the B/P centers and the volumes of the ligand substituted LA counterparts are given in Figure 3.…”

Zintl Lewis Superacids: Al(Ge9L3)3 (L = H, CH3, CHO, CN)

“…which were composed of Zintl ions P 7 3− , ligated with organic species. Not only superalkali but also Zintl clusters ligated with proper ligands can show superhalogen 26 nature. A DFT based study on organo-Zintl-based superatoms 27 also revealed more halogen-mimicking properties of clusters like [Ge 9 (CHO)] and [Ge 9 (CHO) 3 ].…”

Deltahedral Organo‐Zintl Superhalogens

“…prepared a metalloid Zintl cluster (Ga 23 {N(SiMe 3 ) 2 } 11 ) and explained its stability in terms of the Jellium shell model. Recently, Reddy et al . successfully designed deltahedral Ge 9 (R) 3 (R=CF 3 , CN, and NO 2 ) complexes, which exhibit the properties of a superhalogen.…”

“…Hartig et al [21] prepared am etalloid Zintl cluster (Ga 23 {N(SiMe 3 ) 2 } 11 )a nd explained its stabilityi nt erms of the Jellium shell model. Recently,R eddy et al [22] successfully designedd eltahedral Ge 9 (R) 3 (R = CF 3 ,C N, and NO 2 )c omplexes, whiche xhibit the properties of as uperhalogen. In ar ecent review, Sun et al [23] explained how the aromaticity concept can guide the synthesis and analysiso ft he geometrical and electronics tructures of polyanionic Zintl clusters.I nspired by these works, we have attempted to make deltahedralZ intl complexesw ith organic ligands.…”