Inorganic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 30, 2025
A
series
of
structurally
related
bistridentate
heteroleptic
Ru(II)
polypyridyl
complexes,
[RuII(ttpy)(8-HQLS/N/O)]+
(Ru1-Ru3),
were
synthesized,
where
ttpy
=
p-tolyl
terpyridine
and
8-HQLS/N/O
are
monoanionic
N^N^O-donor
tridentate
ligands
(8-HQLX),
derived
from
8-hydroxyquinoline
(8-HQ),
namely,
8-HQLS
2-(2'-benzothiazole)-8-hydroxyquinoline,
8-HQLN
2-(2'-benzimidazole)-8-hydroxyquinoline,
8-HQLO
2-(2'-benzoxazole)-8-hydroxyquinoline.
The
electronic
structures
these
rigid
systematically
tuned
by
varying
the
noncoordinating
heteroatoms
(S,
O,
NH)
in
five-membered
heterocyclic
ring,
impacting
properties,
redox
potentials,
excited-state
lifetime/dynamics,
deactivation
pathways
photophysical
behavior
corresponding
complexes.
Notably,
[RuII(ttpy)(8HQLN)]+
(Ru2)
exhibited
an
lifetime
(τ
>
1
ns
CH3CN
at
RT)
surpassing
that
homoleptic
complex
[Ru(ttpy)2]2+
∼
0.62
ns),
despite
its
more
distorted
octahedral
geometry.
These
complexes
(Ru1-Ru3)
showed
extended
lifetimes
compared
to
their
counterpart
Ru4.
displayed
absorption
red
region,
which
is
favorable
for
phototherapeutic
applications.
Their
relative
singlet
oxygen
(1O2)
quantum
yields
(ΦΔ)
ranged
0.03
0.10.
Given
reasonable
1O2
generation
ability,
demonstrated
potential
as
photocatalysts
organic
substrates,
evidenced
effectiveness
photooxidation
PPh3
Ph3P=O
a
model
reaction.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(61)
Published: Aug. 7, 2023
Light-activated
treatments,
such
as
photodynamic
therapy
(PDT),
provide
temporal
and
spatial
control
over
a
specific
cytotoxic
response
by
exploiting
toxicity
differences
between
irradiated
dark
conditions.
In
this
work,
novel
strategy
for
developing
near
infrared
(NIR)-activatable
Ru(II)
polypyridyl-based
photosensitizers
(PSs)
was
successfully
developed
through
the
incorporation
of
symmetric
heptamethine
cyanine
dyes
in
metal
complex
via
phenanthrimidazole
ligand.
Owing
to
their
strong
absorption
NIR
region,
PSs
could
be
efficiently
photoactivated
with
highly
penetrating
light
(770
nm),
leading
high
photocytotoxicities
towards
several
cancer
cell
lines
under
both
normoxic
hypoxic
Notably,
our
lead
PS
(Ru-Cyn-1),
which
accumulated
mitochondria,
exhibited
good
photocytotoxic
activity
challenging
low-oxygen
concentration
(2
%
O2
)
upon
irradiation
conditions
owing
combination
type
I
II
PDT
mechanisms.
The
fact
that
Protoporphyrin
IX
(PpIX),
metabolite
clinically
approved
5-ALA
PS,
found
inactive
same
positions
Ru-Cyn-1
promising
agent
treatment
deep-seated
tumours.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(14), P. 6202 - 6216
Published: Feb. 22, 2024
Ruthenium(II)
complexes
containing
diimine
ligands
have
contributed
to
the
development
of
agents
for
photoactivated
chemotherapy.
Several
approaches
been
used
obtain
photolabile
Ru(II)
complexes.
The
two
most
explored
use
monodentate
and
incorporation
steric
effects
between
bidentate
Ru(II).
However,
introduction
electronic
in
has
less
explored.
Herein,
we
report
a
systematic
experimental,
theoretical,
photocytotoxicity
study
novel
series
Ru1–Ru5
general
formula
[Ru(phen)2(N∧N′)]2+,
where
N∧N′
are
different
minimal
strained
based
on
1-aryl-4-benzothiazolyl-1,2,3-triazole
(BTAT)
scaffold,
being
CH3
(Ru1),
F
(Ru2),
CF3
(Ru3),
NO2
(Ru4),
N(CH3)2
(Ru5)
substituents
R4
phenyl
ring.
stable
solution
dark,
but
upon
irradiation
water
with
blue
light
(λex
=
465
nm,
4
mW/cm2)
photoejection
ligand
BTAT
was
observed
by
HPLC-MS
spectrometry
UV–vis
spectroscopy,
t1/2
ranging
from
4.5
14.15
min
depending
properties
corresponding
BTAT,
Ru4
(the
one
more
electron
withdrawing
substituent,
NO2).
ground
state
singlet
excited
triplet
using
density
functional
theory
(DFT)
time-dependent
DFT
(TD-DFT)
calculations.
A
mechanism
Ru
complexes,
H2O,
is
proposed.
Phototoxicity
studies
A375
HeLa
human
cancer
cell
lines
showed
that
new
were
strongly
phototoxic.
An
enhancement
emission
intensity
cells
treated
Ru5
response
increasing
doses
due
ligand.
These
suggest
could
serve
as
photocleavable
protecting
group
cytotoxic
bis-aqua
ruthenium
warhead
[Ru(phen)2(OH2)2]2+.
Journal of Computational Chemistry,
Journal Year:
2024,
Volume and Issue:
45(23), P. 2034 - 2041
Published: May 11, 2024
Abstract
The
outcomes
of
DFT‐based
calculations
are
here
reported
to
assess
the
applicability
two
synthesized
polypyridyl
Ru(II)
complexes,
bearing
ethynyl
nile
red
(NR)
on
a
bpy
ligand,
and
analogues,
modified‐NR,
in
photodynamic
therapy.
absorption
spectra,
together
with
non‐radiative
rate
constants
for
S1
–
Tn
intersystem
crossing
transitions,
have
been
computed
this
purpose.
Calculations
evidence
that
structural
modification
chromophore
destabilizes
HOMO
complexes
thus
reducing
H‐L
gap
and,
consequently,
shifting
maximum
wavelength
within
therapeutic
window,
up
620
nm.
Moreover,
favored
ISC
process
from
bright
state
involves
triplet
closest
energy,
which
is
also
characterized
by
highest
SOC
value
involvement
whole
ligand
delocalising
unpaired
electrons.
These
show
photophysical
behavior
dominated
chromophore.
Journal of Medicinal Chemistry,
Journal Year:
2024,
Volume and Issue:
67(7), P. 5902 - 5923
Published: March 23, 2024
Nuclear
factor
kappa
beta
(NF-κB)
plays
a
pivotal
role
in
breast
cancer,
particularly
triple-negative
by
promoting
inflammation,
proliferation,
epithelial–mesenchymal
transition,
metastasis,
and
drug
resistance.
Upregulation
of
NF-κB
boosts
vascular
endothelial
growth
(VEGF)
expression,
assisting
angiogenesis.
The
Ru(II)
complexes
methyl-
dimethylpyrazolyl-benzimidazole
N,N
donors
inhibit
phosphorylation
ser536
p65
translocation
the
heterodimer
(p50/p65)
to
nucleus,
disabling
transcription
upregulate
inflammatory
signaling.
VEGFR2
at
Y1175,
disrupting
downstream
signaling
through
PLC-γ
ERK1/2,
ultimately
suppressing
Ca(II)-signaling.
Partial
release
antiangiogenic
ligand
reactive
oxygen
species-rich
environment
is
possible
as
per
our
observation
both
complexes.
are
nontoxic
zebrafish
embryos
up
50
μM,
but
ligands
show
strong
vivo
activity
3
μM
during
embryonic
Tg(fli1:GFP)
no
visible
effect
on
adult
phase.
Inorganic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(13), P. 3855 - 3876
Published: Jan. 1, 2024
A
new
generation
of
benzimidazole-based
cyclometalated
ruthenium(
ii
)
complexes
with
bpy
or
dpq
as
ancillary
ligands
are
effective
against
hypoxic
cancers
via
green
light
activation
and
can
directly
disrupt
phospholipid
membranes
trigger
oncosis.
Dalton Transactions,
Journal Year:
2024,
Volume and Issue:
53(26), P. 10947 - 10960
Published: Jan. 1, 2024
The
search
for
new
metal-based
anticancer
drug
candidates
is
a
fundamental
task
in
medicinal
inorganic
chemistry.
In
this
work,
we
assessed
the
potential
of
two
Ru(II)-phosphine-mercapto
complexes
as
agents.
complexes,
with
formula
[Ru(bipy)(dppen)(Lx)]PF
Angewandte Chemie,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 13, 2025
Abstract
Photoactivatable
metal
complexes
offer
the
prospect
of
novel
drugs
with
low
side
effects
and
new
mechanisms
action
to
combat
resistance
current
therapy.
We
highlight
recent
progress
in
design
platinum,
ruthenium,
iridium,
gold
other
transition
complexes,
especially
for
applications
as
anticancer
anti‐infective
agents.
In
particular,
understanding
excited
state
chemistry
related
identification
bioactive
species
(excited
metallomics/pharmacophores)
is
important.
metallodrugs
are
classified
here
photocatalysts,
photorelease
agents
ligand‐activated
Their
activation
wavelengths,
cellular
action,
experimental
theoretical
metallomics
states
photoproducts
discussed
explore
strategies
investigation
photoactivatable
metallodrugs.
These
have
potential
clinical
Photodynamic
Therapy
(PDT),
Photoactivated
Chemotherapy
(PACT)
Photothermal
(PTT).
