ic3c02623_si_001.pptx (26.53 MB)
[(OB)2‑M©B7O7‑BO]− (M = Mn, Tc, Re): Chemically Stable and Triply Aromatic Ballet Rotors
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posted on 2023-11-30, 17:35 authored by Bo Jin, Bin Huo, Caixia Yuan, Si-Dian Li, Yan-Bo WuSingle-molecule
nanorotors are generally constructed based on boron
atoms to obtain structural fluxionality via possessing the delocalized
multicenter bonds. However, the electron-deficient boron atoms are
commonly exposed in these nanorotors, which leads to extremely high
chemical reactivity, which blocks the synthesis in the condensed phase.
In this work, we computationally designed a series of transition-metal-doped
boron oxide clusters MB10O10– (in structural configuration of [(OB)2-M©B7O7-BO]−, M = Mn, Tc, Re, © means
“centered” in a planar or quasi-planar hypercoordinate
environment), which can be vividly named as “ballet rotors”
to label their anthropomorphic dynamic rotational behaviors. The rotational
fluxionality in ballet rotors originates from the completely delocalized
nature of the bonding within their MB10 core moieties.
Remarkably, compared with single-molecule nanorotors having bare boron
atoms and the narrow HOMO–LUMO gaps (≤4.00 eV) as well
as low vertical detachment energies (VDEs, ≤4.46 eV for anions),
the ballet rotors possess significantly improved chemical stability,
as evidenced sterically by the absence of exposed boron atoms and
electronically by much wider HOMO–LUMO gaps (5.66–5.98 eV) as well as obviously higher
VDEs between 5.36 and 5.47 eV. Specifically, the ballet rotors are
mainly stabilized by the delicately placed peripheral oxygen atoms,
which can compensate for all electron-deficient boron atoms via O
→ B π back bonds and sterically protect them. Simultaneously,
they are additionally stabilized by aromatic stabilization effect
from possessing the novel S + P + D triple aromaticity. We expect
that the proposal of chemically stable ballet rotors in this work
can arouse the rational design of nanorotors for experimental realization
in the condensed phase.
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generally constructed baseddelocalized multicenter bondscompletely delocalized naturearomatic stabilization effect): chemically stabledeficient boron atomsbare boron atoms7 sub10 subobviously higher vdesexposed boron atomsballet rotors originates66 – 5boron atomsballet rotorscommonly exposed≤ 4© bvividly namedtriple aromaticitystructural configurationsterically protectrotational fluxionalityrational designmainly stabilizedexperimental realizationevidenced stericallycore moietiescondensed phasecomputationally designedbonding withinanions ),additionally stabilized98 ev47 ev46 ev00 ev
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