TY - JOUR
T1 - Deciphering the chemical bonding of the trivalent oxygen atom in oxygen doped graphene
AU - Ugartemendia, Andoni
AU - Casademont-Reig, Irene
AU - Zhao, Lili
AU - Zhang, Zuxian
AU - Frenking, Gernot
AU - Ugalde, Jesus M.
AU - Garcia-Lekue, Aran
AU - Jimenez-Izal, Elisa
N1 - Publisher Copyright:
© 2024 The Royal Society of Chemistry
PY - 2024/3/26
Y1 - 2024/3/26
N2 - Recently, planar and neutral tricoordinated oxygen embedded in graphene has been imaged experimentally (Nat. Commun., 2019, 10, 4570-4577). In this work, this unusual chemical species is studied utilizing a variety of state-of-the-art methods and combining periodic calculations with a fragmental approach. Several factors influencing the stability of trivalent oxygen are identified. A σ-donation and a π-backdonation mechanism between graphite and oxygen is established. π-Local aromaticity, with a delocalized 4c-2e bond involving the oxygen atom and the three nearest carbon atoms aids in the stabilization of this system. In addition, the framework in which the oxygen is embedded is crucial too to the stabilization, helping to delocalize the “extra” electron pair in the virtual orbitals. Based on the understanding gathered in this work, a set of organic molecules containing planar and neutral trivalent oxygen is theoretically proposed for the first time.
AB - Recently, planar and neutral tricoordinated oxygen embedded in graphene has been imaged experimentally (Nat. Commun., 2019, 10, 4570-4577). In this work, this unusual chemical species is studied utilizing a variety of state-of-the-art methods and combining periodic calculations with a fragmental approach. Several factors influencing the stability of trivalent oxygen are identified. A σ-donation and a π-backdonation mechanism between graphite and oxygen is established. π-Local aromaticity, with a delocalized 4c-2e bond involving the oxygen atom and the three nearest carbon atoms aids in the stabilization of this system. In addition, the framework in which the oxygen is embedded is crucial too to the stabilization, helping to delocalize the “extra” electron pair in the virtual orbitals. Based on the understanding gathered in this work, a set of organic molecules containing planar and neutral trivalent oxygen is theoretically proposed for the first time.
UR - http://www.scopus.com/inward/record.url?scp=85189330747&partnerID=8YFLogxK
U2 - 10.1039/d4sc00142g
DO - 10.1039/d4sc00142g
M3 - 文章
AN - SCOPUS:85189330747
SN - 2041-6520
VL - 15
SP - 6151
EP - 6159
JO - Chemical Science
JF - Chemical Science
IS - 16
ER -
