Au102+ and Au₆X42+ clusters: Superatomic molecules bearing an SP³-hybrid Au₆core

Abstract

The octahedral Au 6 core is explored for the formation of novel SP 3 -hybrid superatomic molecules by considering Au 21 10 and Au 6 X 21 4 clusters (X5 F, Cl, Br, I). The bonding between the four capping atoms and the Au 6 core requires a combination of 1S and 1P shells of the core leading to a set of four equivalent hybrid orbitals. Thus, combining the superatom concept with both the Lewis structure model and VSEPR theory contributes to the rationalization of structure and bonding in metal clusters. For example, our results consider the Au 6 X 21 4 clusters as analogues of the simplest perhalogenated hydrocarbon, CX 4 .

Mg3F7: A superhalogen with potential for new nanomaterials design

“…These hypervalent structures were given the name "superhalogens" by Gutsev and Boldyrev who proposed their existence in the early 1980s and have introduced a simple MX k + 1 formula, where M is the main group or the transition metal atom, X is a halogen atom, and k is the maximal formal valence of the atom M. [4] Up to now, a great number of theoretical and experimental studies have been performed to explore new superhalogen species and find ways to increase their application scope. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] The main aim of investigating novel superhalogen systems is to deliver reliable data and predictions considering the possible use of such compounds as electron acceptors (oxidizing agents). Due to their strong oxidizing capability, superhalogens can be used to access the high oxidation states otherwise unreachable in conventional chemistry.…”

Superhalogens as Building Blocks of Super Lewis Acids

“…It is known that the hybridization of superatomic complexes can be determined from the natural localized molecular orbitals(NLMO's) . The hybridization of central B in Lewis acids is of sp 2 type.…”

“…It is known that the hybridization of superatomic complexes can be determined from the natural localized molecular orbitals (NLMO's). [67][68][69] The hybridization of central B in Lewis acids is of sp 2 type. To find similar pattern of hybridization in our studied complexes, we generate NLMO's of B[C 2 BNO(CN) 3 ] 3 and B[C 2 BNS (CN) 3 ] 3 complexes and compare these with BH 3 in Figure 8.…”

[Au12(SR)6]2−, As Smaller 8‐Electron Gold Nanocluster Retaining an SP3‐Core. Evaluation of Bonding and Optical Properties from Relativistic DFT Calculations

“…The computed LMO's of 1 consist of a set of four equivalent orbitals (Figure ) resulting from the combination of the 1S and 1P orbitals (related to atomic sp 3 ‐hybrids) distributing the 8‐ ce in four localized 8c–2e orbitals involving the Au 8 core. They are oriented in a quasi‐tetrahedral disposition denoting the hybridized SP 3 ‐Au 8 core in the [Au 12 (SMe) 6 ] 2− cluster, which can be viewed as a superatomic analogue of classical molecules such as CH 4 ,…”