In Situ Photoconversion of Multicolor Luminescence and Pure White Light Emission Based on Carbon Dot-Supported Supramolecular Assembly

Article abstract of DOI:10.1021/jacs.8b13675

Constructing multicolor photoluminescence materials that allow for the integration of suitable external stimuli in order to control luminescence color conversions is a challenging objective. Multicolor luminescent output that is regulated in an in situ photo-controlled manner is not a common phenomenon. Herein, a photoluminescent supramolecular assembly, prepared in two stages, is described that displays in situ photo-tuning broad-spectrum output. Benefiting from the reversible photo-switched constitutional interconversion of diarylethenes, the fluorescence of a guest molecule, styrylpyridinium-modified diarylethene, can be switched on/off by alternating ultraviolet and visible light irradiation. Upon complexation of this guest with a host, cucurbit[8]uril, the fluorescence intensity of the resulting binary supramolecular nanofiber shows a drastic enhancement when compared with that of the free guest, which can also be quenched and recovered reversibly by light irradiation. Significantly, such cationic supramolecular nanofibers also interact with anionic carbon dots to form broad-spectrum output ternary supramolecular assemblies, the fluorescence of which can be changed efficiently from yellow to blue in an in situ photo-controlled manner. Pure white light emission can be realized expediently in the luminescence color-conversion process. The use of light as an external stimulus to regulate fluorescent color conversion provides us with an opportunity to design and construct more advanced anti-counterfeiting materials as well as visual display instruments.

Full text of DOI:10.1021/jacs.8b13675

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Article
In Situ Photoconversion of Multicolor Luminescence and Pure White Light
Emission Based on Carbon Dot-Supported Supramolecular Assembly
Huang Wu, Yong Chen, Xianyin Dai, Peiyu Li, J. Fraser Stoddart, and Yu Liu
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 12 Mar 2019
Downloaded from http://pubs.acs.org on March 12, 2019
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In Situ Photoconversion of Multicolor Luminescence and Pure White Light
Emission Based on Carbon Dot-Supported Supramolecular Assembly
‡
,†
‡
‡
‡
,†,∇,║
and Yu Liu*,‡,§
Huang Wu, Yong Chen, Xianyin Dai, Peiyu Li, J. Fraser Stoddart*
‡College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, 94
Weijin Road, Nankai District, Tianjin 300071, P.R. China
†Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208,
United States
∇School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia
║Institute for Molecular Design and Synthesis, Tianjin University, 92 Weijin Road, Nankai District,
Tianjin 300072, P.R. China
§Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), 92 Weijin Road,
Nankai District, Tianjin 300072, P. R. China
*
E-mail: stoddart@northwestern.edu
*E-mail: yuliu@nankai.edu.cn
MAIN TEXT
*
Correspondence Address
*Correspondence Address
Professor J Fraser Stoddart
Department of Chemistry
Northwestern University
Professor Yu Liu
Department of Chemistry
Nankai University
2
145 Sheridan Road
94 Weijin Road
Evanston, IL 60208-3113 (USA)
Tel: (+1)-847-491-3793
Tianjin 300071 (CHN)
Tel: (+86)-2350-3625
E-Mail: yuliu@nankai.edu.cn
E-Mail: stoddart@northwestern.edu
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ABSTRACT: Constructing multicolor photoluminescence materials that allow for the
integration of suitable external stimuli in order to control luminescence color conversions is a
challenging objective. Multicolor luminescent output that is regulated in an in situ photo-
controlled manner is not a common phenomenon. Herein, a two-stage assembled
photoluminescence supramolecular assembly is described, that displays in situ phototuning
broad-spectrum output. Benefiting from the reversible photo-switched constitutional
interconversion of diarylethenes, the fluorescence of a guest molecule, styrylpyridinium-
modified diarylethene, can be switched on/off by alternating ultraviolet and visible light
irradiation. Upon complexing with a host，cucurbit[8]uril, the fluorescence intensity of the
resulting binary supramolecular nanofiber shows a drastic enhancement when compared with
that of the free guest, which can also be quenched and recovered reversibly by light irradiation.
Significantly, such cationic supramolecular nanofibers also interact with anionic carbon dots to
form broad-spectrum output ternary supramolecular assemblies, the fluorescence of which can
be changed efficiently from yellow to blue in an in situ photo-controlled manner. Pure white
light emission can be realized expediently in the luminescence color conversion process. The
use of light as an external stimulus to regulate fluorescent color conversion provides us with an
opportunity to design and construct more advanced anti-counterfeiting materials as well as
visual display instruments.
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INTRODUCTION
The construction of multicolor photoluminescence materials that can be tuned in a simple
1
manner has attracted an increasing amount of attention , because of their potential applications
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3
4
as biological image reagents, stretchable displays, multidimensional sensors, photoelectric
5
6
devices, and light-emitting diodes . The conventional methods of acquiring such materials are
mainly physical blending or the covalent connections of chromophores with complementary
7
fluorescence in accurate ratios. Meanwhile, luminescent materials that can be tuned for white-
light emission are particularly important, since they can be applied practically in the fields of
8
visual display media and lighting instruments. Thus far, development of this type of white-
light emission materials is limited by the available preparation protocols or device fabrication
9
techniques. In contrast to the conventional approaches, several noncovalent strategies have
been developed in recent years for the synthesis of multicolor emission materials that respond
1
0
11
to external stimuli. For example, Yam et al. have constructed a new class of amphiphilic
anionic platinum(II) assemblies that display tunable fluorescence emission by variation of
12
solvent polarity. Ito et al. have reported a gold(I) isocyanide complex that exhibits different
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photoluminescent colors, which are interconvertible by treatment with acetone and mechanical
1
3
shearing in the solid state. Tian et al. have utilized two-armed fluorescent molecules as guests
and γ-cyclodextrin as the host to construct novel host−guest complexes, which show multicolor
1
4
luminescence that relies on intramolecular charge transfer. Tao et al. have reported that
various fluorescent emissions can be obtained by adjusting the electronic distributions of the p-
phenylenevinylene units within the hydrophobic cavity of cucurbit[8]uril. The use of external
stimuli to regulate multicolor luminescent output provides a convenient way to construct new
classes of photoluminescence materials. Among these external stimuli, light is of particular
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interest, because of its clean, noninvasive, and remote-controlling nature. Reports of such
fluorescence color conversion processes that regulated in a reversible photo-controlled manner
are still rare.
Among the various building blocks16 for constructing photo-responsive supramolecular
systems, diarylethene derivatives (DAEs), on account of their generally (i) rapid light response,
17
(
ii) no spontaneous thermal reversion, and (iii) outstanding photochromic properties, have led
1
8
19
to many successful applications as optical switches, molecular modulators, helical transfers
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controller, and information storage media. Meanwhile, carbon dots (CDs) are a popular class
of carbon nanomaterials with the promising advantages of non-toxicity, eco-friendliness, high
fluorescence, biocompatibility, good water solubility, excellent photostability, and easy surface
2
2
23
functionalization. CDs have been, therefore, widely utilized as photosensitizers, imaging-
guided nanocarriers,24 multidimensional memory materials,25 and biosensors.26 In this
investigation, a photo-responsive multicolor luminescent supramolecular assembly is
constructed (Scheme 1) from anionic carbon dots (CDs) and cationic supramolecular nanofibers
that are composed of the styrylpyridinium-modified perfluorocyclopentene diarylethene
2
+
derivative 1 and cucurbit[8]uril (CB[8]). On account of the reversible photoisomerization of
the diarylethene unit, the fluorescence of styrylpyridinium-modified diarylethene guest
2+
2+
molecule 1 and the resulting binary supramolecular nanofibers 1 CB[8] can be switched
on/off by alternating ultraviolet and visible light irradiation. Such photo-responsive cationic
supramolecular nanofibers further co-assembled with the anionic CDs to form ternary
supramolecular nanoparticles, which exhibit colorful emission capacitiesi.e., gold, yellow,
khaki, and bluewhile the luminescent colors of the ternary supramolecular assembly can be
interconverted efficiently by irradiated with ultraviolet and visible light. White light emission
is also realized in the fluorescent color conversion process.
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■
RESULTS AND DISCUSSION
Synthetic routes to the guest molecules 1•2Cl / 2•Cl and carbon dots are summarized in
Schemes S1 and S2, respectively. The guest molecule 1•2Cl is obtained in 78% yield by the
condensation of the diarylethene derivative 6 with 4-picolinium iodide, followed by counterion
exchanges. Employing a similar synthetic method, the reference compound 2•Cl with better
water solubility is prepared in 88% yield. The carbon dots are prepared by means of thermal
pyrolysis with citric acid as the carbon source and diethylenetriamine as the surface passivation
agent, followed by amide condensation with succinic anhydride. The UV-vis absorption
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spectrum (Figure 1b) of the open-ring form (OF-1 ) of 1 shows a strong absorption peak at
2+
3
95 nm. After irradiation of aqueous solutions of OF-1 with UV light (254 nm, 2.0 min), the
absorption peak at 395 nm decreases gradually with a blue shift of ~10 nm, and is accompanied
by the appearance of a new absorption band centered on 625 nm. Three clear isosbestic points
are observed at 311, 360, and 465 nm in the UV-vis absorption spectrum. The photocyclization
2+
quantum yield (Φ ) for 1 is determined (Table S1) to be 0.30. In addition, color changes
o-c
(Figure 1a) from pale yellow to blue are observed after UV light irradiating an aqueous solution
2
+
27
2+
of 1 . These phenomena are attributed to (Figure 1a) the transformation of 1 from the open-
2+
2+
ring form (OF-1 ) to the closed-ring form (CF-1 ). When an aqueous solution of the closed-
2
+
2+
ring isomer (CF-1 ) is irradiated with visible light (>600 nm, 1.5 min), the color of the CF-1
solution returns to being pale yellow, and its UV-vis absorption spectrum almost resembles
2
+
2+
(Figure S8) that of OF-1 . When excited at 395 nm, the fluorescence spectrum of 1 reveals
(Figure 1c) an emission peak centered on 560 nm. Upon irradiation with UV light (254 nm, 2.0
2
+
min), the fluorescence intensity of 1 is gradually quenched by 82%, and the fluorescence
quantum yield of 12+ decreased (Table S3) from 0.63% to 0.010%, because of the self-
2
+
absorption effect of CF-1 . The fluorescent on/off quenching ratio (Ron/off) is calculated to be
by comparing the intensity at maximum emission wavelength before and after UV light
irradiation. When the aqueous solution is irradiated with visible light (>600 nm, 1.0 min), the
5
2
+
fluorescence is recovered. These results indicate that the constitution of 1 can go back and
forth between the open-ring and closed-ring isomers upon alternating irradiation with UV and
visible light. The excitation light shows the negligible influence on the photoisomerization
reaction of 12+ under current experimental conditions (Figure S12), but this influence is
inevitable when using a high-intensity excitation light source (Figure S13). Moreover, this
interconversion could be repeated (Figures 1d and S8) for several cycles without appreciable
2
+
light fatigue. The ring-closing conversion yield of 1 is measured (Figure S11a) to be 79%
2
+
2+
upon irradiation with UV light. Furthermore, CF-1 can return quantitatively to OF-1 upon
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irradiation (Figure S11b) with visible light. All these results demonstrate the excellent photo-
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switched constitutional interconversion of 1 .
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Cucurbit[8]uril (CB[8]) , which possesses high binding affinity towards a variety of neutral
or cationic guest molecules, has been used widely as the assembler of supramolecular
architectures in aqueous solutions. It can therefore be anticipated that CB[8] will bind to
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positively charged 1 . The supramolecular assembly consisting of 1 and CB[8] is studied by
UV-vis absorption, NMR, and fluorescence spectroscopies. Upon stepwise addition of CB[8]
2
+
2+
to an aqueous solution of OF-1 , the absorption peak of 1 centered on 395 nm shifts gradually
2
+
(
Figure S14) to 420 nm. The binding constant K between OF-1 and CB[8] is determined
a
7
−1
(
Figure S14, inset) to be 1.19 ×10 M in aqueous solutions. A Job’s plot shows (Figure S15)
2
+
a maxima at a molar fraction of 0.5, indicating 1:1 stoichiometric ratio between OF-1 and
2
+
CB[8]. On account of the high affinity between CB[8] and OF-1 , supramolecular nanofibers
are obtained readily. Transmission electron microscope (TEM, Figure 2b) and atomic force
microscope (AFM, Figure S16) images reveal one dimensional (1D) fine nanofibers with
lengths of several micrometers. The average hydrodynamic diameter has been determined
2
+
(
Figure S17) to be 470 nm upon equimolar mixing of CB[8] and 1 , indicating the formation
of highly polymerized supramolecular assemblies. In order to verify the binding mode of CB[8]
2
+
+
with 1 , reference compound 2 with better water-solubility is synthesized (Figures S5−7). In
1
+
the H NMR spectrum (Figure S18) of a 2:1 mixture of 2 and CB[8], the chemical shifts of the
protons (H and H ) residing on the C=C double bonds and those (H and H ) residing on the
4
5
6
7
phenylene groups show upfield shifts (Δδ = 0.45, 0.42, 0.64, and 0.30 ppm for H , H , H , and
4
5
6
H , respectively). The resonances of the protons (H , H , and H ) residing on the pyridinium
7
1
2
3
rings and those (H and H ) on the thiophene rings are shifted downfield (Δδ = 0.03−0.22 ppm).
8
9
In addition, correlation peaks are observed (Figure S19) between pyridinium protons (H , H ,
1
2
and H ) and thiophene protons (H and H ) in the two-dimensional (2D) ROESY spectrum.
3
8
9
Combining the 1D and 2D NMR spectra, it is clear that CB[8] is bound to the phenylene and
C=C double bond units. Considering the intermolecular steric effect between the pyridinium
2+
and perfluorocyclopentene units in the binary supramolecular assembly OF-1 CB[8], the
2+
bonding mode of OF-1 CB[8] is comfirmed by theoretical calculations using the unilateral
+
styrylpyridinium-modified diarylethene (3 ) as a model compound. The energy optimized
+
structure for the OF-3 CB[8] is determined to be that (Figure S20 and Table S2) in which the
phenylene group and C=C double bond units are included in the cavity of CB[8], which is
1
agreement with the result from H NMR spectroscopy.
2
+
Upon complexation with CB[8], the fluorescence intensity of OF-1 increases (Figure 2a)
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6-fold as compared to the inherent fluorescence of OF-1 , benefiting from the fact that free
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rotation of C=C double bond is restricted by CB[8]. The fluorescence quantum yield of OF-
12+
CB[8] is measured to be 12% (Table S3), a value which is considerably higher than that
0.63%) for free OF-1 . The maximum emission wavelength is shifted bathochromically from
2
+
(
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Furthermore, upon irradiation with the UV light (254 nm, 2.0 min), the fluorescence intensity
2
+
of 1 CB[8] is quenched (Figure 2c) gradually by 97%. The fluorescent on/off quenching ratio
(
Ron/off) is calculated to be 30. The fluorescence quenching can also be detected by the naked
2+
eye, wherein the bright yellow fluorescence of the OF-1 CB[8] gradually turns dark (Figure
2
d, inset) upon irradiation with UV light. When the nonluminous aqueous solution is irradiated
with visible light (>600 nm, 40 s), the yellow fluorescence recovers (Figure 2d, inset). These
2
+
2+
results indicate that the constitutions of 1 can also be interconverted between OF-1 and CF-
12+
in the host-guest complex upon light irradiation. The UV-vis absorption spectra also confirm
the outstanding photo-conversation cycles of 1 CB[8]. Upon irradiating aqueous solutions
2
+
2
+
of OF-1 CB[8] with UV light (254 nm, 2.0 min), the strong absorption peak at 420 nm
decreases gradually (Figure S21) and a new absorption peak appears at 655 nm with a 30 nm
2
+
bathochromic shift compared with that (625 nm) of 1 . The UV-vis absorption spectrum reverts
back to its original state upon visible light irradiation (>600 nm, 1.0 min). These processes can
be repeated (Figure S22) through several cycles without appreciable light fatigue, an
observation which is consistent (Figure 2d) with the fluorescence spectra.
In order to utilize fully the photo-switched fluorescence behavior of the present cationic
2
+
supramolecular assembly 1 CB[8], carbon dots (CDs) are employed as a model substrate in
the construction of a broad-spectrum output luminescent supramolecular material. There are
2+
several inherent advantages of introducing CDs into the 1 CB[8] supramolecular assembly.
(1) The fact that CDs emit bright blue fluorescence, which is complemented by the yellow
2
5
2+
fluorescence of the supramolecular nanofiber 1 CB[8]. (2) The spherical distribution of
charged functional groups on the surface of CDs provide an ideal adhesion agent to promote
2+
the co-assembly with the cationic supramolecular nanofiber, 1 CB[8]. Experimentally, CDs
are prepared by thermal pyrolysis and their morphology is investigated by TEM. A number of
black dots with a size distribution of 4−8 nm are observed in the TEM image (Figure 3a). The
average hydrated radius is 5.5 nm (Figure S23). The high resolution TEM analysis reveals
(
Figure S24) the lattice spacings of CDs to be 0.39 nm and 0.22 nm, corresponding to the
diffraction peaks (Figure S25) centered on 40.2° and 22.5° in the powder X-ray diffraction
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pattern, respectively. This result indicates that the CDs are highly crystalline. The UV-vis
absorption spectrum of the CDs exhibits (Figure S26a) two absorption peaks at 260 and 360
3
2
nm, which can be assigned to the π−π* transitions of the aromatic ring components and the
n−π* transition of the C=O group on the surface of CDs, respectively. When excited at 360 nm,
strong blue fluorescence is observed (Figure 3c, inset). The fluorescence spectrum reveals
(Figure 3c) an emission peak centered on 458 nm, and the corresponding fluorescence quantum
yield (Table S3) is 31%. The fluorescence spectra of the CDs are excitation wavelength- and
pH-dependent. The emission peaks are shifted (Figure 3d) bathochromically from 458 to 537
nm, when the excitation wavelengths are changed from 360 to 480 nm. The fluorescence
intensity increases (Figure S26b) progressively with a change in pH from 2 to 7. There are no
obvious changes in fluorescence intensity upon further enhancing the basicity. The functional
groups on the surface of the CDs have been studied by Fourier transform infrared (FTIR)
spectroscopy and X-ray photoelectron spectroscopy (XPS). The broad vibrational bands in the
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range of 3000−3500 cm can be assigned to O−H and N−H stretching vibrations. The vibration
−1
bands at 1633, 1550, 1417, and 1259 cm can be ascribed to the stretching vibration of C=O,
bending vibration of N−H, and the stretching vibrations of C−N and C−O, respectively (Figure
S27). The XPS spectrum shows (Figure S28) strong signal peaks for the elements C, O, and N.
These results demonstrate that there are a lot of carboxylic acids and amide groups distributed
on the surface of the CDs. In addition, the zeta potentials of the CDs decrease (Figure S29)
gradually from 30.6 to −48.1 mV, when the pH is changed from 2 to 9. In a neutral aqueous
solution, the zeta potential of the CDs (Figure 3b) is −32.3 mV, indicating that the carboxylic
acids are the dominant functional groups on the surface of the CDs.
On account of the good luminescent behavior and the anionic surface functional groups of
2
+
the CDs, the luminescent supramolecular assembly (CDs@1 CB[8]) can be readily
constructed by electrostatic interactions between the cationic supramolecular nanofibers
2
+
1 CB[8] and the anionic CDs. The scanning electron microscopy (SEM) image of the
2
+
supramolecular assembly CDs@1 CB[8] shows (Figure S30b) numerous spherical
nanoparticles with an average diameter of ∼700 nm, consistent with the features observed
(
Figure S30a) in the TEM image. A dynamic light scattering (DLS) experiment reveals (Figure
2+
S31) the average hydrodynamic diameter of the CDs@1 CB[8] nanoparticles to be 757 nm
2
+
in neutral aqueous solution. In addition, the zeta potential of CDs@1 CB[8] supramolecular
nanoparticles is determined (Figure S32) to be −16.9 mV, a value which is higher than that
2
+
(
−32.3 mV) of CDs. All of these results demonstrate consistently that the cationic 1 CB[8]
supramolecular nanofibers are able to co-assemble efficiently with the anionic CDs, courtesy
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of electrostatic interactions. CDs@OF-1 CB[8] exhibit multicolor fluorescence emission.
2+
With the gradual addition of OF-1 CB[8] to the 1 μg/mL aqueous solution of CDs, the
2
+
fluorescence emission peak, centered on 582 nm, derived from 1 CB[8] increases gradually,
and the fluorescence emission peak centered on 458 nm originating from the CDs undergoes
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(
Figure 4a) a slight decrease. The fluorescence colors of the resulting ternary supramolecular
assembly (Figure 4c) change linearly from bright blue to yellow, as indicated by the CIE 1931
chromaticity diagram. It is noteworthy that white-light emission (0.34, 0.33) is observed when
2
+
the concentration of the OF-1 CB[8] supramolecular assembly is ∼1.17 M. The quantum
yield of the resulting white-light emission is ∼6.8%. Benefiting from the reversible photo-
2+
controlled luminescent behavior of 1 CB[8], the fluorescence of the resultant ternary
2+
supramolecular assembly (CDs@1 CB[8]) can also be regulated by alternating UV and
2
+
visible light irradiation. The fluorescence spectra of the CDs@1 CB[8] shows (Figure 4b)
two emission bands centered on 458 and 582 nm, which can be ascribed to the fluorescence
2
+
emissions of CDs and 1 CB[8], respectively. Upon irradiation with UV light (254 nm, 1.5
min), the emission peak centered on 582 nm decreases dramatically, accompanied by a slight
decrease in the emission peak at 458 nm. All of the luminescent color coordinates have been
calculated and plotted (Figure 4d) in the CIE 1931 chromaticity diagram, wherein the
2
+
fluorescence colors of CDs@1 CB[8] change linearly from yellow to blue. The pure white
light emission (0.33, 0.33) is also realized upon UV light irradiation for ∼24 s, and the
2+
2+
2+
corresponding ratio of OF-1 to CF-1 is 32:68. The aqueous solutions of CDs@1 CB[8]
exhibit (Figure 4e) colorful emissionsi.e., gold, yellow, khaki, and bluewith prolonging
the UV light irradiation time. Subsequently, when the solution is irradiated with visible light
(
>600 nm, 30 s), the fluorescence emission of the solution returns to yellow, indicating that the
2+
fluorescence colors of CDs@1 CB[8] can be regulated efficiently by light. In control
2
+
experiments, the emission peak of the binary supramolecular assembly (CDs@OF-1 ) in the
2
+
range of 500 to 700 nm is weaker obviously than that of CDs@OF-1 CB[8] (Figure S33),
2
+
indicating that electrostatic interactions between the CDs and OF-1 do not effectively restrict
2+
the free rotation of C=C double bonds in OF-1 . There is no appreciable change (Figure S34)
2+
of fluorescence color when only the cationic OF-1 is gradually added to the 1 g/mL aqueous
2
+
solution of CDs. Upon irradiation an aqueous solution of CDs@OF-1 with UV light (254 nm,
.5 min), there is also no appreciable change in the fluorescence color (Figure S35). These
1
results confirm that CB[8] is an indispensable component in these spectral tunable luminescent
supramolecular materials. When considering the rational design of supramolecular assembly
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with photo-responsive multicolor luminescence output, there are three main points need to be
considered. (1) The introduction of outstanding photo-responsive components, which are
indispensable for the desired photo-controlled behavior. (2) The complementary fluorescence
color of fluorophores, a factor which is crucial for constructing the broad-spectrum output
materials. (3) The appropriate noncovalent bonding interactions to integrate the fluorophores.
They are important in constructing the multicolor luminescence supramolecular assembly. It is
believed that these design principles, not only provide ideas for designing broad-spectrum
outputs photoluminescence materials, but also serve as a reference for constructing more
advance anti-counterfeiting materials and photo-controlled molecular devices.
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CONCLUSION
A photo-switched multicolor luminescent supramolecular assembly has been realized from
anionic carbon dots and cationic supramolecular nanofibers that are comprised of a
2+
styrylpyridinium-modified diarylethene derivative 1 and cucurbit[8]uril. On account of the
reversible photo-switchable constitutional interconversion properties of dithienylethene, the
fluorescence of 12+ and the binary supramolecular nanofibers can be switched on/off by
alternating UV and visible light irradiation in aqueous solutions. In addition, a ternary
luminescent supramolecular assembly shows multicolor fluorescence emissions, which can be
interconverted efficiently in an in situ photo-controlled manner. Pure white light emission can
also be realized conveniently in the photo-switched luminescence color conversion process.
These smart supramolecular luminescent materials have potential applications in the design and
synthesis of anti-counterfeiting materials and photo-controlled molecular devices.
■
ASSOCIATED CONTENT
Supporting Information
Detailed synthetic procedures, microscopic morphology, and spectroscopic (NMR, HRMS,
UV-vis absorption, and fluorescence) characterization data for the guest molecules 1•2Cl and
2+
2
•Cl, carbon dots (CDs), supramolecular fibers (1 CB[8]) and the ternary supramolecular
2+
assembly (CDs@1 CB[8]). This information is available free of charge via the internet at
http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Author
*
*
E-mail: stoddart@northwestern.edu
E-mail: yuliu@nankai.edu.cn
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Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank National Nature Science Foundation of China (NNSFC, Grant Nos.
1432004, 21672113, 21772099, and 21861132001) for the financial support.
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24) Feng, T.; Ai, X.; An, G.; Yang, P.; Zhao, Y. Charge-Convertible Carbon Dots for
Imaging-Guided Drug Delivery with Enhanced in Vivo Cancer Therapeutic Efficiency. ACS
Nano 2016, 10, 4410–4420.
(25) Li, X.; Xie, Y.; Song, B.; Zhang, H. L.; Chen, H.; Cai, H.; Liu, W.; Tang, Y. A Stimuli-
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Responsive Smart Lanthanide Nanocomposite for Multidimensional Optical Recording and
Encryption. Angew. Chem., Int. Ed. 2017, 56, 2689–2693.
(26) (a) Wang, Y.; Jiang, K.; Zhu, J.; Zhang, L.; Lin, H. A FRET-Based Carbon Dot-MnO2
Nanosheet Architecture for Glutathione Sensing in Human Whole Blood Samples. Chem.
Commun. 2015, 51, 12748–12751. (b) Bui, T. T.; Park, S.-Y. A Carbon Dot–Hemoglobin
Complex-Based Biosensor for Cholesterol Detection. Green Chem. 2016, 18, 4245–4253.
(27) Cheng, H. B.; Zhang, H. Y.; Liu, Y. Dual-Stimulus Luminescent Lanthanide Molecular
Switch Based on an Unsymmetrical Diarylperfluorocyclopentene. J. Am. Chem. Soc. 2013, 135,
10190–10193.
(28) (a) Tian, J.; Zhou, T. Y.; Zhang, S. C.; Aloni, S.; Altoe, M. V.; Xie, S. H.; Wang, H.;
Zhang, D. W.; Zhao, X.; Liu, Y.; Li, Z. T. Three-Dimensional Periodic Supramolecular Organic
Framework Ion Sponge in Water and Microcrystals. Nat. Commun. 2014, 5, 5574. (b) Barrow,
S. J.; Kasera, S.; Rowland, M. J.; del Barrio, J.; Scherman, O. A. Cucurbituril-Based Molecular
Recognition. Chem. Rev. 2015, 115, 12320–12406. (c) Fang, R.; Zhang, H.; Yang, L.; Wang,
H.; Tian, Y.; Zhang, X.; Jiang, L. Supramolecular Self-Assembly Induced Adjustable Multiple
Gating States of Nanofluidic Diodes. J. Am. Chem. Soc. 2016, 138, 16372–16379. (d)
Samanta, S. K.; Moncelet, D.; Briken, V.; Isaacs, L. Metal-Organic Polyhedron Capped with
Cucurbit[8]uril Delivers Doxorubicin to Cancer Cells. J. Am. Chem. Soc. 2016, 138, 14488–
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Murray, J.; Kim, K.; Ogoshi, T.; Yao, W.; Gibb, B. C. The Aqueous
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Extracellular Microenvironment Triggered Targeting and Enhanced Anticancer Drug Delivery.
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H.; Yang, B. Highly Photoluminescent Carbon Dots for Multicolor Patterning, Sensors, and
Bioimaging. Angew. Chem., Int. Ed. 2013, 52, 3953–3957.
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Captions to Scheme and Figures
Scheme 1. Schematic illustration of the in situ photo-switched multicolor luminescence
supramolecular assembly.
2
+
Figure 1. (a) Structural formulas and photographic image of the changes of 1 upon alternating
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irradiation with UV and visible light. (b) UV-vis absorption spectra and (inset) absorbance
2
+
2+
−5
intensity changes of OF-1 at 625 nm ([OF-1 ] = 2.0 × 10 M, 298 K) upon irradiation with
UV light (254 nm, 2.0 min). (c) Emission spectra and (inset) emission intensity changes of OF-
12+
at 560 nm ([OF-1 ] = 5.0 × 10 M, λ = 395 nm, 298 K) upon irradiation with UV light
2+
−6
ex
2
+
2+
–5
(
254 nm, 2.0 min). (d) Absorbance changes at 625 nm of 1 ([1 ] = 2.0 × 10 M, 298 K) upon
alternating irradiation with UV (254 nm, 2.0 min) and visible (>600 nm, 1.5 min) light in
aqueous solutions.
2
+
Figure 2. (a) Emission spectra and (inset) emission intensity changes of OF-1 at 582 nm
2
+
−6
−6
(
[OF-1 ] = 5.0 × 10 M, [CB[8]] = 0−10.5 × 10 M, λ = 395 nm, 298 K) upon gradual
ex
2+
addition of CB[8] in an aqueous solution. (b) TEM image of OF-1 CB[8] supramolecular
2
+
assembly. (c) Emission spectra and (inset) emission intensity changes of OF-1 CB[8] at 582
2
+
−6
nm ([OF-1 CB[8]] = 5.0 × 10 M, λ = 395 nm, 298 K) upon irradiation with UV light (254
ex
2
+
nm, 2.0 min). (d) Emission spectra and (inset) emission intensity changes of OF-1 CB[8] at
2+
−6
5
82 nm ([OF-1 CB[8]] = 5.0 × 10 M, λ = 395 nm, 298 K) upon alternating irradiation
ex
with UV (254 nm, 2.0 min) and visible light (>600 nm, 40 s) in an aqueous solution.
Figure 3. (a) TEM image of the anionic CDs. (b) Zeta potential of the anionic CDs in a neutral
aqueous solution. (c) Excitation and emission spectra of the anionic CDs ([CDs] = 3 μg/mL,
2
98 K). (d) Emission spectra of the anionic CDs ([CDs] = 3 μg/mL, 298 K) at various excitation
wavelengths in a neutral aqueous solution.
2
+
−6
Figure 4. (a) Emission spectra of CDs ([CDs] = 1 μg/mL, [OF-1 CB[8]] = 0−3 × 10 M,
2
+
λ = 360 nm, 298 K) with gradual addition of OF-1 CB[8] in a neutral aqueous solution. (b)
ex
2
+
2+
−6
Emission spectral changes of CDs@1 CB[8] ([CDs] = 1 μg/mL, [OF-1 CB[8]] = 3 × 10
M, λ = 360 nm, 298 K) upon irradiation with UV light (254 nm, 1.5 min) in a neutral aqueous
ex
solution. (c) The 1931 CIE chromaticity diagram illustrating the luminescent color changes of
2+
CDs with the gradual addition of OF-1 CB[8], corresponding to (a). (d) The 1931 CIE
2
+
chromaticity diagram depicting the luminescent color changes of CDs@1 CB[8] upon
irradiation with UV light (254 nm, 1.5 min), corresponding to (b). (e) Fluorescence photographs
2
+
2+
−6
of CDs@1 CB[8] ([CDs] = 3 μg/mL, [OF-1 CB[8])] = 9 × 10 M) with increasing the
UV light (254 nm, 1.5 min) irradiation time in a neutral aqueous solution.
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