OH-Detected Aromatic Microsolvation of an Organic NO Radical: Halogenation Controls the Solvation Side
The Journal of Physical Chemistry A,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 30, 2025
The
persistent
organic
radical
2,2,6,6-tetramethylpiperidinyloxyl
(TEMPO)
protects
its
NO
center
by
four
methyl
groups.
Two
of
them
are
arranged
tightly
(t)
on
one
side
the
six-membered
puckered
heterocycle,
and
other
two
more
openly
(o)
side.
It
is
shown
OH
stretching
infrared
spectroscopy
in
heated
supersonic
jet
expansions
that
hydrogen
bond
aromatic
ring
a
first
solvating
benzyl
alcohol
have
almost
no
preference
for
either
An
increased
t
develops
para-halogenated
alcohols,
it
inverted
ortho-halogenated
alcohols.
experimental
dependence
actual
halogen
(Cl,
Br,
I)
weak,
whereas
different
quantum
chemical
approaches
predict
or
less
pronounced
trends
along
series.
Some
pre-expansion
reservoir
reduces
TEMPO
to
closed-shell
heterocyclic
hydroxylamine
TEMPO-H
(1-hydroxy-2,2,6,6-tetramethylpiperidine),
extent
TEMPO-H···TEMPO
complex
observed
as
an
impurity.
Language: Английский
Advancing CO2 absorbents through structural innovation: Implementation of the aromatic multi-ring based nucleophilic structure
Seon Ho Kim,
No information about this author
Jihun Ju,
No information about this author
Jaehan Jo
No information about this author
et al.
Chemical Engineering Journal,
Journal Year:
2025,
Volume and Issue:
512, P. 162328 - 162328
Published: April 14, 2025
Language: Английский
Self-aggregation and microhydration mechanisms of monoethanolamine: Far-infrared identification of large-amplitude hydrogen bond libration
The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
161(15)
Published: Oct. 15, 2024
The
strong
tendency
for
self-aggregation
together
with
an
intriguing
mechanism
the
microhydration
of
monoethanolamine
(MEA)
have
been
explored
by
low-temperature
far-infrared
cluster
spectroscopy
in
doped
neon
"quantum"
matrices
at
4
K
complemented
high-level
quantum
chemical
modeling.
In
addition
to
assignment
new
mid-infrared
perturbed
intramolecular
transitions,
a
distinct
transition
is
unambiguously
assigned
concerted
large-amplitude
hydrogen
bond
librational
motion
MEA
homodimer.
This
observation
confirms
global
"head-to-head"
intermolecular
potential
energy
minimum
associated
formation
compact
doubly
OH⋯N
hydrogen-bonded
cyclic
structure,
where
both
monomeric
bonds
are
broken
upon
complexation.
By
means
relative
mixing
ratio
dependencies,
dedicated
annealing
procedures,
and
selective
complexation
between
isotopic
H216O
H218O
samples,
transitions
intra-molecular
hindered
OH
torsional
inter-molecular
H2O
(hindered
c-type
overall
rotational)
monohydrate
furthermore
first
time.
These
spectroscopic
observations
reveal
metastable
conformation,
acts
as
OH⋯O
donor
hydroxy
group
instead
amino
cryogenic
environment,
strengthens
due
cooperativity.
Language: Английский
Self-Association and Microhydration of Phenol: Identification of Large-Amplitude Hydrogen Bond Librational Modes
Molecules,
Journal Year:
2024,
Volume and Issue:
29(13), P. 3012 - 3012
Published: June 25, 2024
The
self-association
mechanisms
of
phenol
have
represented
long-standing
challenges
to
quantum
chemical
methodologies
owing
the
competition
between
strongly
directional
intermolecular
hydrogen
bonding,
weaker
non-directional
London
dispersion
forces
and
C-H⋯π
interactions
aromatic
rings.
present
work
explores
these
subtle
relevance
for
biological
molecular
recognition
processes
via
spectroscopic
observations
large-amplitude
bond
librational
modes
cluster
molecules
embedded
in
inert
neon
"quantum"
matrices
complemented
by
domain-based
local
pair
natural
orbital-coupled
DLPNO-CCSD(T)
theory.
spectral
signatures
confirm
a
primarily
O-H⋯H
hydrogen-bonded
structure
dimer
strengthened
further
cooperative
contributions
from
inter-ring
as
supported
DLPNO-based
energy
decomposition
(LED)
predictions.
In
same
way,
bands
observed
trimeric
molecule
pseudo-
Language: Английский