TY - JOUR
T1 - Exploring the Potential Energy Surface of Trimetallic Deltahedral Zintl Ions
T2 - Lowest-Energy [Sn6Ge2Bi]3- and [(Sn6Ge2Bi)2]4- Structures
AU - Báez-Grez, Rodrigo
AU - Garza, Jorge
AU - Vásquez-Espinal, Alejandro
AU - Osorio, Edison
AU - Rabanal-León, Walter A.
AU - Yañez, Osvaldo
AU - Tiznado, William
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/8/5
Y1 - 2019/8/5
N2 - The synthesis and structural characterization of the dimer [(Sn6Ge2Bi)2]4- raise the possibility of obtaining a broad variety of analogous compounds with different Sn/Ge/Bi proportions. Several combinations of nine atoms have been detected by electrospray mass spectrometry as potential assembly units. However, [(Sn6Ge2Bi)2]4- remains as the unique experimentally characterized species in this series. This fact has motivated us to explore its potential energy surface, as well as its monomers' [Sn6Ge2Bi]3-/2-, in an effort to gain insight into the factors that might be privileging the experimental viability of this species. Our results show that the lowest-energy [Sn6Ge2Bi]3- structure remains in its oxidized product [Sn6Ge2Bi]2-, which corresponds to that identified in the dimer [(Sn6Ge2Bi)2]4-. Additionally, local minima, very close in energy to the lowest-energy monomer, are chiral mixtures that dimerize into diverse structures with a probable energetic cost, making them noncompetitive isomers. Finally, the global minimum of the dimer [(Sn6Ge2Bi)2]4- presents the most stable monomers as assembly units. These results show the importance of considering the simultaneity of all of these conditions for the viability of these types of compounds.
AB - The synthesis and structural characterization of the dimer [(Sn6Ge2Bi)2]4- raise the possibility of obtaining a broad variety of analogous compounds with different Sn/Ge/Bi proportions. Several combinations of nine atoms have been detected by electrospray mass spectrometry as potential assembly units. However, [(Sn6Ge2Bi)2]4- remains as the unique experimentally characterized species in this series. This fact has motivated us to explore its potential energy surface, as well as its monomers' [Sn6Ge2Bi]3-/2-, in an effort to gain insight into the factors that might be privileging the experimental viability of this species. Our results show that the lowest-energy [Sn6Ge2Bi]3- structure remains in its oxidized product [Sn6Ge2Bi]2-, which corresponds to that identified in the dimer [(Sn6Ge2Bi)2]4-. Additionally, local minima, very close in energy to the lowest-energy monomer, are chiral mixtures that dimerize into diverse structures with a probable energetic cost, making them noncompetitive isomers. Finally, the global minimum of the dimer [(Sn6Ge2Bi)2]4- presents the most stable monomers as assembly units. These results show the importance of considering the simultaneity of all of these conditions for the viability of these types of compounds.
UR - http://www.scopus.com/inward/record.url?scp=85070876717&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.9b01206
DO - 10.1021/acs.inorgchem.9b01206
M3 - Article
C2 - 31287671
AN - SCOPUS:85070876717
SN - 0020-1669
VL - 58
SP - 10057
EP - 10064
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 15
ER -