pubs.acs.

org/JPCL Letter

All in One: Stimuli-Responsive, Efficient Mitotracking, and Single

Source White Light Emission
Bibhisan Roy,* Mallu Chenna Reddy, Gregor P. Jose, Felix C. Niemeyer, Jens Voskuhl,*
and Partha Hazra*
Cite This: J. Phys. Chem. Lett. 2021, 12, 1162−1168 Read Online

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ABSTRACT: “All in one” type luminogens, possessing combined properties related to optical,
materials, and biological implications, are of urgent demand today, mainly because of the
combined application potential of such probes. To the best of our knowledge, until now, an “all
in one” type white light emitter together with stimuli-responsive behavior and highly efficient
mitochondrial-tracking ability has not been reported yet. In this contribution, for the first time,
we have investigated a pair of luminogens exhibiting white light emission (CIE coordinates:
0.35, 0.35 (DPAEOA) and 0.29, 0.33 (DPAPMI)) with temperature-induced mechanochromic
features of a centrosymmetrically packed probe (space group P−1). Most importantly, despite
being neutral, our designed probe DPAEOA can specifically illuminate mitochondria with the
highest Pearson coefficient value (0.93), which is rare, as almost all the commercially developed
mitotrackers are cationic fluorophores. Thus, this study will pave a new avenue for the design of
next generation “all in one” type organic luminogens exhibiting potential applications in notable
optical, materials, and biological fields.

“All in one” type next generation luminophores comprising
optical (single component white light emission), materials
(mechanochromic color change), and biological (neutral
mitotracker) implications have not been developed yet.
Hence, the study of single component white light emitters
(SCWLEs) with potential applications in materials science and
biology is a hot topic in recent times.1−5 Typically, SCWLEs
rely on multicomponent systems, as white light emission
(WLE) requires simultaneous emission of the three primary
(red, green, and blue, i.e., RGB) or at least two complementary
(yellow and blue, i.e., YB) colors.1−3,5 SCWLEs offer
numerous decisive advantages over multicomponent systems,
such as better stability, exact reproducibility, and simple
fabrication processes, to name just a few.1−3,5 However,
SCWLEs are difficult to achieve due to their specific
requirements of different emission wavelengths (RGB/YB).
In recent years, a few attempts have been undertaken to
achieve SCWLEs based on excited-state intramolecular proton
transfer (ESIPT),6 conformational isomerization processes,7
charge transfer (CT),8 and other excited state mechanisms.9,10
Of these, utilization of CT molecules may be promising to
create multifunctional SCWLEs possessing application poten-
tial also for materials. Moreover, CT molecules can be used in
various biological applications, including mitochondria track-
ing. This is because precisely designed CT probes may have
the potential to enter preferably into the cellular mitochondria,
despite the absence of permanent cationic charges, which in
contrary is the required feature for the commercially available
mitotrackers. This attempt can be realized due to the large
membrane potential (ΔΨm) inside the mitochondria.11 The
high ΔΨm arises from its constant oxidization of substrates,
which maintains an excellent “proton gradient” across the lipid
bilayer.11 Owing to this large membrane potential gradient,
mitochondria can take up cationic species (almost all
mitotrackers developed so far are cationic)12 efficiently.
Cationic mitotrackers mostly suffer from poor photostability
under laser irradiation.11,12 This cannot be overcome by using
higher fluorophore concentrations, as this may lead to
destructive aggregation-caused quenching (ACQ) assemblies.
In this context, CT probes are potential candidates to
overcome this and may be used as next generation
mitotrackers. CT probes are able to create intramolecular
partial “positive” and “negative” segments using electron rich
donors and electron dearth acceptors in suitable polar solvent
medium. Considering the presence of large water contents in in
vivo tissues and the high polarity index of water (10.2),
mitochondria would preferably stabilize the CT states. Hence,
in this contribution; we aim to develop charge transfer,
photostable, white light emitters with enhanced water
solubility for bioapplications. Based on an isoindolinone
acceptor core, we have designed three featured compounds
Received: November 24, 2020
Accepted: January 18, 2021

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.jpclett.0c03489

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bearing no donor (EOA) or using diphenylamine (DPAEOA)
and carbazole (CEOA) as donors (Scheme 1).
Scheme 1. −CO2Et Based Designed Probes Investigated in
This Contribution (Left) and Structure of −SO2Ph
Attached Probes (DPAPMI) from Previous Work13 Taken
for Comparison Purpose (Right)
All designed compounds consist of ethyl acrylate (−CO2Et)
moieties, which probably is the main reason for the enhanced
solubility in water (0.41 mM) in contrast to the hydrophobic
phenyl vinyl sulfone (PVS) containing probes described before
(Scheme 1).13 Most intriguingly, the flexible DPA containing
newly designed DPAEOA and the previously reported
DPAPMI13 shows single source pure white light emission in
acetone or chloroform, respectively. The constructed Commis-
sion Internationale de l’éclairage (CIE, 1931) coordinates reveal
white light emission (0.35, 0.35) of DPAEOA in acetone and
Figure 1. Emission profiles of DPAEOA exciting at 330 nm. The arrow beside the legend indicates the order of the polarity. We have provided the
cuvette emission color under the 365 nm excitation for 10 μM of DPAEOA molecules containing in each sample (top panel). From the cuvette
color images, it is clear that in highly polar solvent molecules are poorly emissive, i.e., low quantum yield.
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DPAPMI in chloroform (0.29, 0.33) at similar concentrations
(100 μM). Such small organic molecule based SCWLEs are
rare and difficult to achieve based on two complementary color
combinations. Notably, our designed probe DPAEOA, which is
exhibiting white light emissive properties, is one of the major
developments as an “optical” feature out of the three targeted
“triad” features to design an “all in one” type next generation
probe. In this Letter, our second noteworthy advancement
from the “biological” perspective is the ability of our molecule
to track specifically mitochondria. Newly developed partially
water-soluble DPAEOA was found to illuminate specifically the
mitochondria section of HEK 293 cells with high efficiency
(Pearson coefficient 0.93, discussed in a later part) despite
being a neutral molecule. Herein, our third development from
the “material” standpoint is the mechanochromic color change
of centrosymmetrically packed organic probes. Mechanical
color change from solid state centrosymmetric packed (space
groups P−1 and P21/c etc.) organic luminogens is difficult.14
This Letter provides a glimpse of mechanochromic events
from centrosymmetric packing (space group P−1) of designed
organic molecules. To the best of our knowledge, such an “all
in one” type molecule exhibiting interesting optical and
material properties along with important biological implication
is not yet explored. Thus, we believe that this Letter will
provide suitable platforms to design next generation
luminophore, which will be interesting for researchers working
in the optical, material and biological fields.
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All the newly designed molecules were synthesized by a
functional group interconversion (FGI) followed by oxidative
cyclization of substituted benzonitrile with ethyl acrylate (EA)
in the presence of the Ru metal as a precatalyst {RuCl2(p-
cymene)}2, silver salt (AgSbF6), and Cu(OAc)2·H2O in acetic
acid (for details, see the Supporting Information).
First, to check the electronic features of the newly designed
molecules, DFT calculations have been undertaken (Figure
S1). For the donor substituted molecules (DPAEOA and
CEOA), the HOMO and LUMO electron densities were
mostly found to reside on the donor (DPA and carbazole) and
acceptor (isoindolinone) moieties, respectively, although a
slight overlap on the aryl ring of isoindolinone is observed
particularly for DPAEOA. However, we believe that such a
small overlap will minutely affect the charge-transfer possibility
from the donor to the acceptor. Hence, there may be an
electronic transition from the donor (D) to the acceptor (A)
supporting the intramolecular charge transfer (CT) character
of our designed molecules, namely, DPAEOA and CEOA.
Moreover, we have also calculated absorption spectra of the
newly designed DPAEOA and CEOA probe using the
Minnesota functional (m06hf), which is known as the best
functional for TDDFT calculations.15 The calculated absorp-
tion profile (Figure S26) also consists of our experimental
absorption bands (Figure S21). To verify the theoretical
results, we carried out solvatochromic studies. In the emission
profile of the parent EOA, only a single locally excited (LE)
state or Franck−Condon emission band at ∼380−450 nm was
observed in almost all solvents, which did not show any red
shift upon increasing of the solvent polarity (Figure S2).
However, DPAEOA and CEOA showed a higher energy LE
peak and a lower energy CT peak in various solvents (Figure
1). DPAEOA in toluene exhibited two peaks, where the higher
energy peak (at around ∼400 nm) corresponds to the emission
from the locally excited (LE) state and the lower energy peak
(>500 nm) is assigned to the emission from the CT state
(Figure 1). The higher intensity of the CT peak compared to
the LE peak may be explained as higher population of CT state
compared to the LE state based on a flip-flop motion (see note
S2 in the Supporting Information) of the DPA moiety. Both
these LE and CT peaks are getting red-shifted with the
increase in polarity; however, the extent of red-shift is more
pronounced in the case of the CT state compared to the LE
state. Considering this observation, we anticipated that the LE
state is also having some charge character, and it also supports
our theoretical study where slight overlap between HOMO
and LUMO is observed. Notably, the intensity of the CT state
diminished as the polarity increased (although the population
of CT increases). Here, we believed that the CT state of
DPAEOA is stabilized by the polar solvents significantly,
leading to a decrease in the energy gap between this state and
the ground state. Hence, nonradiative deactivation rate
constants become larger, which is in accordance with the
energy gap law.16,17 This causes the efficient quenching
observed in polar solvents. The reason for this is that if the
solvent polarity further increased (beyond DCM), the
emission profile of DPAEOA consists of only a red-shifted
LE peak along with a shoulder CT peak at ∼600 nm (see DMF
and acetone in Figure 1). When the polarity was further
increased (see MeCN and MeOH), the emission profile
consisted of only LE peak. This is attributed to the very weak
emission intensity of the CT state in highly polar solvents,
which is also evident from the observed weak emission profile
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collected by exciting (Figure S3, λex = 405 nm) at the red end
side of the absorption spectra (Figure S21) to avoid the LE
state excitation. Similarly, we have recorded spectra of CEOA
in different solvents (Figure 1), and it is also following the
same trend as that of DPAEOA. However, the peak positions
and shifts of emission spectra are slightly different probably
due to the different donor ability and less flip-flop motion of
the carbazole moiety compared to the DPA moiety of
DPAEOA. In summary, dual emission along with distinct
intensities and color suggest that our molecules are tunable CT
probes followed by LE excitation. Moreover, the observed long
nanosecond lifetime of our designed probes both in solution
and solid state (Figure S25) infers that the emission coming
out from a stable CT state.
Single crystals of DPAEOA and CEOA suitable for X-ray
diffraction have been grown from equal mixtures of DCM and
MeOH at room temperature (crystallographic information has
been provided in the Supporting Information). The packing
analysis suggests that DPAEOA and CEOA both exhibit
antiparallel stacking, centrosymmetric P-1 space group, and
complex 2D “distorted herringbone” and cross mode packing,
respectively (Figures 2, S4, and S5). Interestingly, these probes
Figure 2. Slipped stacked and cross stacked packing of DPAEOA and
CEOA as obtained by single crystal X-ray diffraction.
exhibit numerous noncovalent interactions. For example,
DPAEOA exhibits CO···H−C (2.353 Å, 2.545 Å), C−
H···π (2.875 Å, 2.736 Å), C−H···H−C (2.388 Å), and C−H···
O (2.545 Å) (Figure S6). CEOA exhibits π···π (3.266 Å), C
H···π (2.766 Å), and C−H···O (2.544 Å, 2.474 Å). (Figure
S6). We attempted to determine these noncovalent inter-
actions using Hirshfeld surface analysis (Note S1, Figures S7
and S8). These interactions and packing patterns (centrosym-
metric/noncentrosymmetric) are the main parameter for
mechanochromic color change in the solid state. Upon
mechanical stress, the associated energy will be released due
to rupturing of these interactions by creating metastable energy
states. For example, C−H···π and van der Waals (H···H)
interactions will release an enthalpy of ∼10.3 and ∼0.4−4 kJ/
mol, respectively.18 Despite numerous noncovalent interac-
tions, the stimuli-responsiveness at room temperature of
DPAEOA and CEOA is hard to be activate. This is mainly
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Figure 3. (A) Emission spectra of DPAEOA (λex = 365 nm) in acetone at different concentrations. (B) CIE coordinates of DPAEOA in acetone
upon excitation at 365 nm at different concentrations. Inset shows a cuvette of DPAEOA in acetone under 365 nm irradiation at concentration of
100 μM.
due to the centrosymmetric packing assisted “zero gross”
dipole moment and “degenerate” electronic energy states of
the molecule in the solid state.19 However, we have previously
gained experience of activating such centrosymmetrically
packed luminogens (space group P21/c and P−1) via thermally
induced crystal phase changes.19 Hence, by utilizing our
previous concept, we have first measured differential scanning
calorimetry (DSC) (Figure S9) of both probes to find the
temperature induced crystal phase changes. Based on the DSC
thermogram, we have heated DPAEOA and CEOA at ∼160
and ∼75 °C, respectively, by taking them on a quartz slide.
After cooling to room temperature followed by slight grinding
with a spatula, both compounds show green to yellow
(DPAEOA) and cyan to green (CEOA) color change along
with a bathochromic shift in the emission profile with respect
to the pristine state (Figures S10 and S11).
The dual emission of LE (blue range) and CT (yellow
range) states of the designed probes prompted us to check the
possibility WLE generation based on yellow, blue (YB)
complementary color combination. Hence, we have invested
much effort to find WLE in various media. Here it is pertinent
to mention that the nature of the dual emission is found to be
highly dependent on both the concentration and polarity of the
solvent and on the excitation energy (Figures 3, S12, and S13).
Therefore, finding a suitable solvent, concentration, and proper
excitation energy is crucial to achieve white light emission in
our system. Notably, to find suitable solvent(s) for achieving
WLE, we have progressed systematically based on the
observation of constructed solvent dependent CIE diagrams
of DPAEOA and DPAPMI (Figures S12 and S14). Solvent
dependent CIE studies of DPAEOA (Figure S13) infer that
probably CHCl3 and acetone will be suitable solvents to
achieve pure white light under a certain concentration, as
coordinates of these solvents are found to reside very close to
pure white light coordinates (0.33, 0.33) in the CIE diagram
(Figure S12). Interestingly, a systematic concentration depend-
ent study of DPAEOA in acetone revealed pure white light
emission (0.35, 0.35 at 100 μM) in acetone (quantum yield ∼
10%) upon excitation at 365 nm (Figure3), which was not
achieved in chloroform at 100 μM (Figure S18). In contrast to
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the case of DPAEOA, based on the solvent dependent CIE
diagram of DPAPMI, it can be seen that chloroform may be
the right solvent to achieve white light emission (Figure S14).
Interestingly, a concentration dependent study of DPAPMI in
chloroform revealed almost pure WLE (0.29, 0.33, quantum
yield ∼13%) (Figure S15). However, like the case of
DPAEOA, the WLE of DPAPMI in chloroform is found to
be extremely sensitive toward concentration as well as
excitation energy. For example, at 100 μM concentration,
DPAPMI showed WLE (0.29, 0.33) upon excitation at 365 nm
(Figure S15), but, upon excitation at 395 nm, the same sample
showed yellow emission (0.42, 0.45) (Figure S16). We found
that the WLE of DPAPMI can be seen by the naked eye over a
wide range of concentrations starting from 100 to 25 μM
owing to the balanced contribution of LE and CT states in
CHCl3 (Figure S15). However, at lower concentration (5
μM), DPAPMI showed near white emission (0.25, 0.28) in
CHCl3 upon excitation at 365 nm but weak yellow emission at
395 nm (Figures S15 and S16). We have further tried to
achieve WLE in the solid state using poly(methyl meth-
acrylate) (PMMA) films doped with our probes. Although we
believe that it will be possible to achieve WLE for both
DPAEOA and DPAPMI in the solid state, as they exhibit the
dual LE and CT emissions likewise in the solution state, it is
extremely hard to get the suitable populations of LE and CT
states to yield WLE in polymeric film. Notably, it requires
multiple trials to achieve the exact population for getting white
light emission. However, we have provided here glimpses that
the slight change of concentration (0.25−1 wt %) of DPAPMI
is able to change its color significantly (Figure S19). Therefore,
we believe at a suitable weight percent, the DPAEOA and
DPAPMI will show WLE in the solid state also, which remains
a scope for future study. In summary, WLE of this molecule is
very specific, and it depends on concentration, polarity, and
excitation energy.
Mitochondria plays major role for energy cycles by
production of ATP via a series of electron-transport reactions
pathways. Mitochondria also generates reactive oxygen species
(ROS), leading the cell death, which is known as the
mitochondria-mediated apoptosis process.20 To get insights
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The Journal of Physical Chemistry Letters
in the study of this apoptosis processes, the exact tracking of
mitochondria is extremely essential. From this context, light
emissive probes that can selectively enter and illuminate the
cellular mitochondrial part are highly important. It is important
to mention that the constant oxidization of substrates in
mitochondria maintains an impressive proton gradient across
the lipid bilayer with a very large membrane potential (ΔΨm)
of around −180 mV (negative inside), which drives the
accumulation of cationic probes preferentially in the
mitochondrial matrix than on the plasma membrane with a
membrane potential of 30−60 mV (negative inside).12,21 As a
result, a very large concentration of cationic probes get
accumulated inside mitochondria (nearly 500-fold) than any
other part of the cell.22 Due to this reason, almost all
developed mitotrackers are based on cationic fluorophores
such as MitoTracker Red (MTR), MitoTracker green (MTG),
and Rhodamine 123.23 However, the diluted solutions of
cationic mitotrackers suffer from poor photostability.12 Hence,
a neutral efficient, photostable, mitotracker is very important.
Considering partial water solubility and the neutral structure of
our compounds, inspired us to study the mitochondria imaging
using our designed molecules. Interestingly, we have observed
that, among the two designed probes, only DPAEOA shows an
exceptional ability to target mitochondria specifically, despite
their neutral structures, which is scarcely reported in the
literature.24−26 Notably, this is the first report on the ester
based perfect neutral mitotracker. Interestingly, only DPAEOA
incubated HEK 293 cells (for details, see the Supporting
Information) are found to exhibit efficient cellular uptake
(Figure 4) with respect to the CEOA treated cells possibly due
to the efficient rotational restriction effect of two aryl rotors of
the DPAEOA luminogen. That is why we have observed very
weak fluorescence intensity of CEOA when incubated with
HEK 293 cells (Figure 4A). In order to compare the ability of
tracking of the DPAEOA molecule with the traditional
Figure 4. (A) Confocal images of DMSO control, DPAEOA, and
CEOA. (B) Overlay mitotracking images of DPAEOA along with
MitoTracker Red.
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mitotracker staining dyes, the dual labeling of HEK 293 cells
was carried out using DPAEOA and MitoTracker Red (Figure
4B). Surprisingly, fluorescence of the DPAEOA is found to be
colocalized with that of the MitoTracker Red fluorescence
(Figure 4B). Notably, the Pearson coefficient (Pearson
coefficient (PC) calculation provides a statistical way to
quantify colocalization, and a PC value closer to 1 indicates a
significant colocalization) is found to be 0.93 (Figure S20),
and it is the highest value compared to another recently
reported Pearson coefficient value (0.90) for neutral drug.24
This result is intriguing as the designed probe does not contain
permanent cationic charges like those of conventional
mitotrackers available on the market. We believe there are
three major reasons to enter specifically mitochondria despite
not having permanent cationic charges of our designed probe.
The first one is the presence of a pendant ester arm, which is
well-known to render the molecule cell permeable, and also it
increases the water solubility of the probe.27 Second, being a
donor−acceptor probe, DPAEOA will contain the permanent
oxidation potential which helps the molecule to specifically
accumulate at the mitochondria bearing large membrane
potential (ΔΨm). Nitrogen heterocycles with N−H bonds can
improve the mitochondrial targeting ability of partial neutral
fluorophores.24
In conclusion, we have developed and investigated small
organic white light emitters (CIE coordinates: 0.35, 0.35
(DPAEOA) and 0.29, 0.33 (DPAPMI)) that possess
thermoinduced mechanochromic materials features. More
interestingly, one of the luminogens (DPAEOA) shows an
exceptional ability to target specifically mitochondria with a
high Pearson coefficient (0.93), despite their noncationic
structures. This observation is rare, as almost all the
commercially developed mitotrackers are cationic fluoro-
phores. To the best of our knowledge, such an “all in one”
type single source white light emitter with stimuli-response and
specific mitochondria tracking ability is not reported yet. Thus,
we believe this study will put forward the fundamental
development idea of “all in one” type fluorescent probes
exhibiting the optical, materials, and biological applications
triad.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpclett.0c03489.
Experimental section, mechanism, synthesis and charac-
terization, NMR data, crystallographic table, DFT, TD-
DFT data, solvatochromic data, absorption spectra,
crystallographic figures, Hirshfeld surface analysis,
DSC, mechanochromism, temperature dependent
study, PXRD data, CIE coordinates, Pearson’s coef-
ficient calculation, as well as notes S1 and S2 (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Partha Hazra − Department of Chemistry, Indian Institute of
Science Education and Research (IISER), Pune, Maharashtra
411008, India; orcid.org/0000-0003-0422-1399;
Email: p.hazra@iiserpune.ac.in
Bibhisan Roy − Department of Chemistry, Indian Institute of
Science Education and Research (IISER), Pune, Maharashtra
411008, India; Faculty of Chemistry (Organic Chemistry)
https://dx.doi.org/10.1021/acs.jpclett.0c03489
J. Phys. Chem. Lett. 2021, 12, 1162−1168
The Journal of Physical Chemistry Letters
and CENIDE, University of Duisburg-Essen, 45141 Essen,
Germany; Email: bibhisan.roy@students.iiserpune.ac.in,
bibhisan.roy@uni-due.de
Jens Voskuhl − Faculty of Chemistry (Organic Chemistry)
and CENIDE, University of Duisburg-Essen, 45141 Essen,
Germany; Email: jens.voskuhl@uni-due.de
Authors
Mallu Chenna Reddy − Department of Chemistry, Indian
Institute of Science Education and Research (IISER), Pune,
Maharashtra 411008, India
Gregor P. Jose − Department of Biological Sciences, Indian
Institute of Science Education and Research (IISER), Pune,
Maharashtra 411008, India
Felix C. Niemeyer − Faculty of Chemistry (Organic
Chemistry) and CENIDE, University of Duisburg-Essen,
45141 Essen, Germany
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpclett.0c03489
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
P.H. acknowledges the Science and Engineering Research
Board (SERB), Government of India (CRG/2020/00567) for
financial support. Jan Balszuweit, Justin Dubbert, Subrata
Nath, Dietrich Tönnes, and Florian Malotke are acknowledged
for their help during various experimental measurements. We
are indebted to the anonymous reviewers for their suggestions.
■
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