d-AO spherical aromaticity in Ce6O8.
After the first introduction of π aromaticity in chemistry to explain the bonding, structure, and reactivity of benzene and its derivatives, this concept was further applied to many other compounds featuring other types of aromaticity (i.e., σ, δ). Thus far, there have been no reports on d-AO-based spherical σ aromaticity. Here, we predict a highly stable bare Ce6O8 cluster of a spherical shape using evolutionary algorithm USPEX and DFT + U calculations. Natural bond orbital analysis, adaptive natural density partitioning algorithm, electron localization function, and partial charge plots demonstrate that bare Ce6O8 cluster exhibits d-AO spherical σ aromaticity, thus explaining its exotic geometry and stability. Ce6O8 complex plays an important role in many reactions and is known to exist in many forms, such as in NH4[Ce6(μ(3)O)5(μ(3)OH)3(μ(2)-C6H5COO)9(NO3)3(DMF)3]*DMF*H2O compound, which is prepared under room temperature, and acts as an oxidizing agent.
Department of Problems of Physics and Energetics, Moscow Institute of Physics and Technology, 9 Institutskiy Land, Dolgoprudny City, Moscow Region, 141700, Russia.
Xiaohu
X
Yu
Department of Problems of Physics and Energetics, Moscow Institute of Physics and Technology, 9 Institutskiy Land, Dolgoprudny City, Moscow Region, 141700, Russia.|Skolkovo Institute of Science and Technology, Skolkovo Innovation Center, 5 Nobel St., Moscow, 143026, Russia.|Department of Geosciences and Center for Materials by Design, Stony Brook University, Stony Brook, New York, 11794.|International Center for Materials Discovery, School of Materials Science, Northwestern Polytechnical University, Xi'an, 720072, China.
Artem R
AR
Oganov
Department of Chemistry and Biochemistry, Utah State University, Logan, Utah, 84322.
Ivan A
IA
Popov
Department of Chemistry and Biochemistry, Utah State University, Logan, Utah, 84322.
Alexander I
AI
Boldyrev
Ce6O8; chemical bonding; d-AO aromaticity; evolutionary program; natural bond orbital analysis