Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(6), С. 2726 - 2734
Опубликована: Янв. 10, 2022
Excited-state
intramolecular
proton
transfer
(ESIPT)
molecules
demonstrating
specific
enol-keto
tautomerism
and
the
related
photoluminescence
(PL)
switch
have
wide
applications
in
displaying,
sensing,
imaging,
lasing,
etc.
However,
an
ESIPT-attributed
coordination
polymer
showing
alternative
PL
between
thermally
activated
fluorescence
(TAF)
long
persistent
luminescence
(LPL)
has
never
been
explored.
Herein,
we
report
assembly
of
a
dynamic
Cd(II)
(LIFM-101)
from
ESIPT-type
ligand,
HPI2C
(5-(2-(2-hydroxyphenyl)-4,5-diphenyl-1H-imidazol-1-yl)isophthalic
acid).
For
first
time,
TAF
and/or
color-tuned
LPL
can
be
achieved
by
controlling
temperature
under
guidance
ESIPT
excited
states.
Noteworthily,
twisted
structure
ligand
LIFM-101
achieves
effective
mixture
higher-energy
states,
leading
to
ISC
(intersystem
crossing)/RISC
(reverse
intersystem
crossing)
energy
high-lying
keto-triplet
state
(Tn(K*))
singlet
(S1(K*)).
Meanwhile,
experimental
theoretical
results
manifest
occurrence
probability
relevance
among
RISC,
ISC,
internal
conversion
(IC)
this
unique
polymer,
unprecedented
TAF/LPL
switching
mechanism,
paving
way
for
future
design
application
advanced
optical
materials.
Accounts of Chemical Research,
Год журнала:
2017,
Номер
50(2), С. 366 - 375
Опубликована: Янв. 9, 2017
ConspectusFluorescent
environment-sensitive
probes
are
specially
designed
dyes
that
change
their
fluorescence
intensity
(fluorogenic
dyes)
or
color
(e.g.,
solvatochromic
in
response
to
microenvironment
polarity,
viscosity,
and
molecular
order.
The
studies
of
the
past
decade,
including
those
our
group,
have
shown
these
molecules
become
universal
tools
sensing
imaging.
In
fact,
any
biomolecular
interaction
organization
results
modification
local
microenvironment,
which
can
be
directly
monitored
by
types
probes.
this
Account,
main
examples
summarized
according
design
concepts.
Solvatochromic
constitute
a
large
class
polarity.
Generally,
they
push–pull
undergoing
intramolecular
charge
transfer.
Emission
highly
polarized
excited
state
shifts
red
more
polar
solvents.
Excited-state
proton
transfer
is
second
key
concept
efficient
dyes,
respond
changing
relative
two
emissive
tautomeric
forms.
Due
sensitivity
polarity
hydration,
been
successfully
applied
biological
membranes
for
studying
lipid
domains
(rafts),
apoptosis
endocytosis.
As
fluorescent
labels,
detect
practically
type
interactions,
involving
proteins,
nucleic
acids
biomembranes,
because
binding
event
excludes
water
from
site.
On
other
hand,
fluorogenic
usually
exploit
rotation
(conformation
change)
as
concept,
with
rotors
being
representatives.
These
were
particularly
imaging
viscosity
order
biomembranes
well
light
up
targets,
such
antibodies,
aptamers
receptors.
emerging
concepts
achieve
include
ground-state
isomerization,
aggregation-caused
quenching,
aggregation-induced
emission.
isomerization
exploits,
instance,
polarity-dependent
spiro-lactone
formation
silica-rhodamines.
quenching
uses
disruption
self-quenched
dimers
nanoassemblies
less
environments
biomolecules.
emission
couples
target
recognition
dye
aggregates.
Overall,
enable
background-free
bioimaging
wash-free
conditions
quantitative
analysis
when
combined
advanced
microscopy,
lifetime
(FLIM)
ratiometric
Further
development
should
address
some
remaining
problems:
(i)
improving
optical
properties,
especially
brightness,
photostability,
far-red
near-infrared
operating
range;
(ii)
minimizing
nonspecific
interactions
systems;
(iii)
adaptation
microscopies,
notably
superresolution
vivo
Chemical Society Reviews,
Год журнала:
2015,
Номер
45(1), С. 169 - 202
Опубликована: Окт. 27, 2015
The
state-of-the-art
of
ESIPT-inspired
solid
state
emitters
and
their
photophysical
properties
applications
in
recent
5
years
were
systematically
reviewed.
Accounts of Chemical Research,
Год журнала:
2018,
Номер
51(7), С. 1681 - 1690
Опубликована: Июнь 15, 2018
ConspectusAs
one
of
the
most
fundamental
processes,
excited-state
proton
transfer
(ESPT)
plays
a
major
role
in
both
chemical
and
biological
systems.
In
past
several
decades,
experimental
theoretical
studies
on
ESPT
systems
have
attracted
considerable
attention
because
their
tremendous
potential
fluorescent
probes,
imaging,
white-light-emitting
materials,
organic
optoelectronic
materials.
is
related
to
fluorescence
properties
usually
occurs
an
ultrafast
time
scale
at
or
below
100
fs.
Consequently,
steady-state
femtosecond
time-resolved
absorption,
fluorescence,
vibrational
spectra
been
used
explore
mechanism
ESPT.
However,
based
previous
studies,
direct
information,
such
as
transition
state
geometries,
energy
barrier,
surface
(PES)
reaction,
difficult
obtain.
These
data
are
important
for
unravelling
detailed
reaction
can
be
obtained
from
state-of-the-art
ab
initio
calculations.In
recent
years,
increasing
number
led
progress.
This
Account
presents
advances
mainly
those
our
group.
We
focus
cases
where
great
importance
indispensable,
resolving
debate
stepwise
concerted
double
(ESDPT),
revealing
sensing
chemosensors,
illustrating
effect
intermolecular
hydrogen
bonding
intramolecular
(ESIPT)
investigating
quenching
by
twisting
process,
determining
size
solute·(solvent)n
cluster
solvent-assisted
reaction.
Through
calculation
vertical
excitation
energies,
optimization
construction
PES
reactions,
we
provide
modifications
experimentally
proposed
mechanisms
completely
new
mechanism.
Our
inspirational
successfully
explain
results;
some
further
confirmed
provided
guidance
researchers
design
chemosensors.Determination
barrier
accurate
key
with
methods.
approach
becomes
complicated
when
charge
involved
time-dependent
density
functional
theory
(TDDFT)
method
optimally
tuned
range-separated
TDDFT
provides
alternative
way.
To
unveil
driving
force
molecular
dynamics
combined
intrinsic
coordinate
calculations
employed.
advanced
approaches
should
Accounts of Chemical Research,
Год журнала:
2020,
Номер
53(2), С. 485 - 495
Опубликована: Янв. 30, 2020
ConspectusEmissive
species
are
powerful
for
luminescent
detection
with
high
sensitivity
and
simple
procedure
light-emitting
diode
(LED)
lighting
because
of
their
efficiency,
long
lifetime,
low
energy
consumption.
Here
we
propose
the
concept
multiple
luminescence
emissions
from
a
single
matrix
or
under
single-wavelength
excitation.
Multiemission
not
only
realizes
sensing
but
also
possesses
capacity
self-reference
environment-free
interferences.
The
color
change
is
convenient
visible
detection.
In
multiemission
species,
every
emissive
center
responds
to
specific
analyte
improve
efficiency
multiple-target
extends
applications
anticounterfeiting,
colorful
LEDs,
information
storage.
To
date,
it
still
challenging
combine
more
than
one
type
in
species.
Obtaining
excitation
needs
exquisite
design.Metal–organic
frameworks
(MOFs)
porous
hybrid
assemblies
prepared
metal
ions
organic
ligands.
Metal
nodes
ligands
large
π-conjugated
systems
have
potential
construction
MOFs.
Abundant
diverse
precursors
provide
possibility
prepare
MOFs
emissions.
pores
channels
act
as
hosts
encapsulate
guest
additional
sites.In
this
Account,
multiple-luminescence
(ML-MOFs)
summarize
recent
research
progress
on
designs,
constructions,
reported
by
our
group
others.
ML-MOFs
that
possess
Six
different
kinds
strategies
introduced:
(1)
both
MOFs;
(2)
use
mixed-metal
centers
(3)
combination
whole
achieve
application;
(4)
host–guest
after
encapsulation
species;
(5)
organization
MOF
multiemission;
(6)
exhibiting
dual
emission
ML-MOFs.
We
discuss
mechanisms
realize
excitation,
such
antenna
effect
excited-state
intramolecular
proton
transfer.
ratiometric
sensing,
LED
lighting,
storage
summarized.
With
hope
spark
new
ideas
inspire
endeavors
design
ML-MOFs,
especially
postsynthetic
techniques
modification,
exchange,
deprotection,
promote
storage,
Chemical Reviews,
Год журнала:
2016,
Номер
117(16), С. 10826 - 10939
Опубликована: Дек. 13, 2016
Ultrafast
photochemical
reactions
in
liquids
occur
on
similar
or
shorter
time
scales
compared
to
the
equilibration
of
optically
populated
excited
state.
This
involves
relaxation
intramolecular
and/or
solvent
modes.
As
a
consequence,
reaction
dynamics
are
no
longer
exponential,
cannot
be
quantified
by
rate
constants,
and
may
depend
excitation
wavelength
contrary
slower
processes
occurring
from
equilibrated
states.
Such
ultrafast
photoinduced
do
obey
Kasha–Vavilov
rule.
Nonequilibrium
effects
also
observed
diffusion-controlled
intermolecular
directly
after
photoexcitation,
their
proper
description
gives
access
intrinsic
that
normally
hidden
diffusion.
Here
we
discuss
these
topics
relation
organic
homogeneous
liquids.
Discussed
include
intra-
electron-
proton-transfer
processes,
as
well
photochromic
with
without
bond
breaking
formation,
namely
ring-opening
cis–trans
isomerizations,
respectively.
Chemical Reviews,
Год журнала:
2017,
Номер
117(21), С. 13353 - 13381
Опубликована: Окт. 9, 2017
This
paper
provides
a
systematic
review
and
analysis
of
different
phenomena
that
violate
basic
principle,
Kasha's
rule,
when
applied
to
photochemical
reactions.
In
contrast
the
classical
route
ultrafast
transition
lowest
energy
excited
state
reaction
starting
therein,
in
some
cases,
these
reactions
proceed
directly
from
high-energy
states.
Nowadays,
this
phenomenon
can
be
observed
for
number
major
types
excited-state
reactions:
harvesting
product
via
intersystem
crossing;
photoisomerizations;
bond-breaking;
electron,
proton,
transfers.
We
show
specific
conditions
their
observation
are
determined
by
kinetic
factors.
They
should
among
fastest
studied
systems,
competing
with
vibrational
relaxation
radiative
or
nonradiative
processes
occurring
upper
The
anti-Kasha
effects,
which
provide
an
important
element
sheds
light
on
mechanisms
transformations,
open
new
possibilities
selective
control
variety
practical
applications.
Efficient
utilization
excess
electronic
enhance
performance
systems
artificial
photosynthesis
photovoltaic
devices.
modulation
reporting
signal
excitation
lead
technologies
optical
sensing
imaging.
Journal of the American Chemical Society,
Год журнала:
2015,
Номер
137(26), С. 8509 - 8520
Опубликована: Июнь 15, 2015
A
tailored
strategy
is
utilized
to
modify
5,10-dimethylphenazine
(DMP)
donor-acceptor
type
N,N'-disubstituted-dihydrodibenzo[a,c]phenazines.
The
representative
compounds
DMAC
(N,N'-dimethyl),
DPAC
(N,N'-diphenyl),
and
FlPAC
(N-phenyl-N'-fluorenyl)
reveal
significant
nonplanar
distortions
(i.e.,
a
saddle
shape)
remarkably
large
Stokes-shifted
emission
independent
of
the
solvent
polarity.
For
with
higher
steric
hindrance
on
N,N'-substituents,
normal
also
appears,
for
which
peak
wavelength
reveals
solvent-polarity
dependence.
These
unique
photophysical
behaviors
are
rationalized
by
electronic
configuration
coupled
conformation
changes
en
route
geometry
planarization
in
excited
state.
This
proposed
mechanism
different
from
symmetry
rule
imposed
explain
anomalously
long-wavelength
DMP
firmly
supported
polarity-,
viscosity-,
temperature-dependent
steady-state
nanosecond
time-resolved
spectroscopy.
Together
femtosecond
early
dynamics
computational
simulation
reaction
energy
surfaces,
results
lead
us
establish
sequential,
three-step
kinetics.
Upon
excitation
N,N'-disubstituted-dihydrodibenzo[a,c]phenazines,
intramolecular
charge-transfer
takes
place,
followed
combination
polarization
stabilization
skeletal
motion
toward
planarization,
i.e.,
elongation
π-delocalization
over
benzo[a,c]phenazines
moiety.
Along
encounter
raised
N,N'-disubstitutes,
resulting
local
minimum
state,
intermediate.
initial
intermediate,
final
state
renders
full
spectrum
interest
significance
their
anomalous
photophysics.
Depending
rigidity,
N,N'-disubstituted-dihydrodibenzo[a,c]phenazines
exhibit
multiple
emissions,
can
be
widely
tuned
red
deep
blue
even
white
light
generation
upon
optimization
surrounding
media.