Tetraphenylethylene(TPE)-Containing Metal-Organic Nanobelt and Its Turn-on Fluorescence for Sulfide (S2-)

Article abstract of DOI:10.1021/acs.inorgchem.0c00928

A metal-organic supramolecular nanobelt was synthesized by quantitative self-assembling terpyridine-functionized tetraphenylethylene (TPE) and Cd²⁺, which only showed a weak emission both in solution or aggregated state. Nevertheless, nanobelt

Full text of DOI:10.1021/acs.inorgchem.0c00928

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Tetraphenylethylene(TPE)-Containing Metal−Organic Nanobelt and
Its Turn-on Fluorescence for Sulfide (S2−)
Kaixiu Li,# Zhengguang Li,# Die Liu,* Mingzhao Chen, Shi-Cheng Wang, Yi-Tsu Chan,
and Pingshan Wang*
Cite This: https://dx.doi.org/10.1021/acs.inorgchem.0c00928
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ABSTRACT: A metal−organic supramolecular nanobelt was synthesized by
quantitative self-assembling terpyridine-functionized tetraphenylethylene
(TPE) and Cd2+, which only showed a weak emission both in solution or
aggregated state. Nevertheless, nanobelt complex could be transferred to a
fluorescence turn-on sensor to S2− by taking advantage of the structural
transformation from nanobelt to its fluorescent ligand.
architecture was weak and/or not emissive was meaningful,
because such a system could serve as fluorescent sensors
resulting from the structural transformation. Further, the fact
that the complexes in solid state were non-/weak-emissive
facilitates the practical applications as fluorescent turn-on
sensors, wherein responsive molecules exists in aggregation
form.19 Herein, the tetrapodal TPE-terpyridine ligands were
synthesized and showed intense AIE effect. But, unexpectedly,
the assembled metal−organic nanobelt and corresponding
aggregates were weakly luminous. Based on these results, the
nanoaggregates system was constructed and displayed obvious
stimuli-responsive emission enhancement for S2−.
INTRODUCTION
■
Tetraphenylethene (TPE) was a typical aggregation-induced
emission (AIE) luminogen, which was first put forward by
Tang and colleagues,1 and a variety of AIE materials based on
TPE have been developed and utilized in various areas.2−5
Facilitated by the highly directional and predictable feature of
coordination-driven self-assembly, rationally incorporating
TPE moiety to ligands is an alternative strategy to obtain a
metal−organic supramolecular structure with desired optical
properties.6−11 There are two methods to construct such an
assembled structure. One method is the anchoring of the TPE
moiety on ligands as an attachment, in which the resultant
metallo-assembly showed expected AIE properties.12−14 The
other is the use of the TPE unit as the rigid skeleton to
generate the 2D and 3D supramolecular architecture.5,7,15,16 By
the subtle designing of the shape of ligand and assembled
architecture, the resultant complexes showed unique emissive
behavior due to the restriction of intramolecular rotation
(RIR) resulting from the metal-coordination.15,17 Recently, the
pure white-light emission from a metallo-rosettes in both
solution and aggregation states was developed by incorporating
the TPE fluorophores.12 Stang et al. found that the emissive
behavior of supramolecular coordination complexes was
affected by subtle structural factors, in which the fused
rhomboid structure displayed a weaker fluorescence than the
fused triangle in dilute solutions, while the result was reversed
for the aggregated state.18 All of above complexes showed
intense emission in solution or in the aggregation state. But,
obtaining the TPE-containing supramolecular aggregates in
which ligands showed strong emission while the metallo-
RESULTS AND DISCUSSION
■
As shown in Scheme 1, tetrapodal ligand L was designed and
synthesized utilizing the 4-fold Suzuki coupling of 1,1,2,2-
tetrakis(4-bromophenyl)ethene and 4′-(4-boronatophenyl)-
1
tpy. The structure of L was verified by H NMR, in which a
set of signals corresponding to terpyridine moiety was shown,
including one characteristic singlet at 8.75 ppm assigned to the
H3′,5′ and two doublets and two triplets attributed to the
H3,3′′, H6,6′′ and H4,4′′, H5,5′′, respectively (Figure 1a).
Received: March 29, 2020
https://dx.doi.org/10.1021/acs.inorgchem.0c00928
© XXXX American Chemical Society
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Scheme 1. Illustration of the Self-Assembly of Metal-Organic Nanobelt S
Figure 1. (a) 1H NMR spectra (500 MHz) of L (top) in CDCl3 (* for CHCl3) and self-assembled nanobelt S (bottom) in CD3CN. (b) ESI-MS
and (c) 2D ESI-MS plot (m/z vs drift time) of S. The charge states of intact assemblies are marked, and the inset corresponds to energy-minimized
structure.
Furthermore, the peak observed from electrospray ionization
mass spectrum (ESI-MS) was found at 781.816 (cal. 781.809)
contributed to [M + 2H]2+, demonstrating the successful
synthesis of ligand L (Figure S4).
change, in which the downfield-shift from 8.75 to 8.92 ppm of
characteristic tpyH3′,5′ was clearly observed resulting from the
electron-withdrawing effect upon coordination, and the
dramatic upfield-shift from 8.67 to 7.92 ppm of tpyH6,6′′ was
also distinctly observed owing to the electron shielding effect
from metal ions.20 Additionally, only one set of sharp proton
signals of the terpyridine unit with an identical integrated ratio
was displayed, demonstrating formation of single and discrete
The self-assembly of nanobelt was performed by mixing L
and Cd(NO3)2 with a precise stoichiometric ratio (1:2) in
−
CHCl3/CH3OH. After counterion exchange with PF6 , the
nanobelt structure S was afforded in 93% yield (Scheme 1).
As shown in Figure 1a, the resultant assembled product was
initially characterized by the NMR spectrum. In comparison to
the ligand L, the resonance signals of complex S displayed clear
1
assembled structure. All of H NMR peaks were fully assigned
by means of correlated spectroscopy (2D COSY) (Figure S7).
B
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Importantly, the ESI-TWIM-MS, served as the 2D MS
analysis, was used to verify the desired structure. As displayed
in Figure 1c, the single species of charged signals (z = 6+ to
10+) with narrow drift time distributions was exclusively
observed, indicative of the absence of any superimposed
fragments or overlapping isomers or conformers. Derived from
the ESI-TWIM-MS datum, an average collision cross section
(CCS) was determined to be 808.97 20.29 Å2, which was
coincident with the simulated results (Table S1).
More information for the size of the nanobelt structure S
were obtained by the diffusion-ordered NMR spectroscopy
(DOSY) and dynamic light scattering (DLS) experiments. All
of the relevant signals of complex S in the DOSY spectrum
were in a narrow band with the diffusion coefficient (D) of
3.02 × 10−10 m2 s−1 (Figure 2a), indicating the creation of a
single assembly. The dynamic radius was calculated to be 1.97
nm using the Stokes−Einstein equation, which consisted well
with the sizes of energy-minimized structures from molecular
modeling (Figure S11), demonstrating the formation of a
desired nanobelt structure. Furthermore, the radius of nanobelt
S was determined to be 3.2 nm from the DLS experiments
(Figure 2b), which was also matched with the molecule
structure.
The absorption spectrum of ligand L in dilute CHCl3
showed an intense band centered at 280 nm with molar
absorption coefficients (ε) of 1.27 × 105 M−1 cm−1 assigned to
ligand-centered (LC) π−π* transitions (Figure 3a). In
comparison with the ligand, the complex S in dilute MeCN
has a more intense band at 287 nm with molar absorption
Figure 2. (a) DOSY spectrum of complex S in CD3CN and (b) DLS
datum of complex S in CH3CN with various H2O fractions (c = 7.04
× 10−6 M).
Further, the ESI-MS of complex S showed just a series of
clear peaks with sequential charge states from 5+ to 10+ that
contributed to the structure by losing different numbers of
−
PF6 (Figure 1b). The experimental isotope patterns of each
signal were in good accordance with the corresponding
theoretical one, unambiguously supporting the composition
of desired nanobelt [L3Cd6] (Figure 1b, Figure S10).
Figure 3. (a) UV−vis spectra, (c) fluorescence emission spectra (λex = 360 nm; slit width: ex = 5 nm, em = 2.5 nm), and (e) photographs upon
excitation at 365 nm of ligand L versus CH3OH fraction in 2 mL CHCl3/CH3OH mixtures (c = 1.6 × 10−5 M). (b) UV−vis spectrum, (d)
fluorescence emission spectra (λex = 320 nm; slit width: ex = 5 nm, em = 5 nm), and (f) photographs upon excitation at 365 nm of complex S
versus H2O fraction in 2 mL CH3CN/H2O mixtures (c = 7.04 × 10−6 M).
C
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was proved by the DLS results, in which the average
hydrodynamic diameters (Dh) were measured to be 16, 24,
32, 122, and 164 nm with 10%, 30%, 50%, 70%, and 90% H2O,
respectively (Figure 2b). Tetraphenylethene (TPE) is a typical
aggregation-induced emission (AIE) luminogen, which is
nonemissive in solution but shows intense emission in
aggregated state. Unexpectedly, complex S exhibited weak
emission in aggregated state. Complex S possesses a rigid 3D
structure by complexing with metal ions to form a nanobelt.
We speculated that such rigid 3D structure of complex S
hinders compact packing and the conformation of TPE units
might not be intensely affected even in aggregated state, as a
result to negligible AIE phenomenon.23,24
Tpy-Cd complexes were unstable and prone to disassemble
to tpy ligands under alkaline conditions or S2− existing due to
the formation of insoluble cadmium salt. Based on this fact,
herein, the aggregates of complex S were explored as a
fluorescence turn-on sensor responsive to S2−. Initially,
fluorescence turn-on experiments were performed in
CH3CN/H2O (v/v, 1/9) mixture, but the fluorescence
intensity could not be accurately measured due to the fact
that obvious precipitates were formed after adding analysts
(Figure S17). Thus, the complex S in CH3CN/H2O (v/v, 1/1)
mixture was chosen as the experimental subject, and the
volume of each experiment was 2.0 mL. As described in Figure
4a, after 4.0 μmol of various salts (KBr, KI, KNO3, Na2SO4,
NaCl, NH4Cl, NH4BF4, CH3COOK, NaHCO3, Na2CO3,
Na2S) was added to aggregates in CH3CN/H2O (v/v,1/1),
complex S showed a specific emission enhancement response
to alkali salt (CH3COOK, NaHCO3, Na2CO3) and Na2S.
Corresponding fluorescent emission spectroscopies showed a
16-, 45-, 31-, and 51-fold enhancement for analyst CH3COOK,
NaHCO3, Na2CO3, and Na2S, respectively. In contrast, no
obvious fluorescence enhancement was found from other
analysts, and the slight emission increase for Br−, Cl−, and I−
was probably resulting from further aggregation via partly
disassembly lead by halogen ions coordination (Figure 4b).25
Such results were supported by the UV−vis spectroscopies, in
Figure 4. Fluorescence responses of complex S in 2 mL of CH3CN/
H2O at 298 K (v/v, 1/1; c = 7.04 × 10−6 M): (a) the photographs (λex
= 365 nm) and (b) the relative fluorescence intensity of after and
before addition of 4.0 μmol interfering species; c) fluorescence
spectra after adding different concentrations of Na2S (λex = 320 nm;
slit width: ex = 5 nm, em = 5 nm).
−
2−
coeffucients (ε) of 2.57 × 105 M−1 cm−1 and two distinct
absorption bands at ∼322 and ∼334 nm (Figure 3b), which
are assigned to intraligand charge transfer (ILCT).21 To
further research the light-emitting behavior of ligand L and
assembled nanobelt S, the UV−vis and fluorescence spectra
were determined in mixed solvent with the different fraction of
poor solvent. As shown in Figure 3c, Figure 3e, and Figure S13,
the ligand L displayed weak luminescence in CHCl3 and there
was no obvious change with gradually increasing methanol or
hexane fraction from 10% to 70% due to its solubility;
however, the fluorescence intensities displayed obvious
enhancement with 90% CH3OH or hexane fraction. As we
expected, such result was attributed to the AIE effect of TPE-
containing L. As observed from Figure 3a and Figure S12, the
formation of aggregates with 90% CH3OH or hexane was
verified by the decrease of high-energy bands at 283 nm and
increase of low-energy tailing bands in the absorption spectra
due to the π−π stacking interactions.22 Moving to complex S,
which was nonluminescent in dilute CH3CN, just a slight
emission enhancement was observed with gradually increasing
methanol or water fraction from 10% to 90% (Figure S15,
Figure 3d, and Figure 3f). Surely, as observed from Figure 3f,
the aggregates were obviously formed with 90% water,
supported by the UV−vis spectra in which a similar change
to the ligand was observed. Further, the aggregates forming
which no considerable change was observed for NO3 , SO4
,
and BF4− and where there was a decrease of high-energy bands
at 283 nm and an increase of low-energy tailing bands for Br−,
Cl−, and I− (Figure S18). Further, the characteristic ILCT
band around 330 nm was still observed for other analysts;
however, it disappeared for NaHCO3, Na2CO3, and Na2S,
demonstrating that complex S was disassembled to ligands
(Figure S18). Further, the 1H NMR spectra displayed that the
signals assigned to complex S fully disappeared and that the
ligand L was formed after adding Na2S, suggesting that Na2S
was able to disassemble the complex to form the ligands
(Figures S8 and S9).
As displayed in Figure S23, time-dependent fluorescence
spectra of complex S with excess S2− (4.0 umol) were recorded
in 2.0 mL of CH3CN/H2O (1/1, v/v). As the reaction
proceeded, the emission at 494 nm rapidly increased before 90
s elapsed. From 90 to 1100 s, the rate of fluorescence
enhancement gradually decreases to close to 0 over time
(Figure S24). Further, the concentration-dependent fluores-
cence enhancement was determined by fluorescence titration
experiments (Figure 4c). Upon the progressive addition of
Na2S to complex S in 2.0 mL of CH3CN/H2O (1/1, v/v), the
fluorescence intensity at 494 nm gradually increased. There
was good linearity between the fluorescence intensity and the
concentration of the Na2S in the 0−1.0 × 10−3 M range
D
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(Figure S22), supporting that complex S was a good candidate
Yi-Tsu Chan − Department of Chemistry, National Taiwan
University, Taipei 10617, Taiwan; orcid.org/0000-0001-
9658-2188
for quantitative detection of the S2−.
CONCLUSION
■
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c00928
In summary, an uncommon metal−organic supramolecular
nanobelt was synthesized by the self-assembly of TPE-
containing tetrapodal ligand with Cd2+. As expected, the
terpyridine ligands in aggregation state showed intense
emission due to the AIE effect of TPE moieties; however,
the complex S exhibited weak emission both in solution or in
aggregates. Based on this fact, the complex S was developed as
a fluorescence turn-on sensor to detect S2− by taking advantage
of the structural transformation from nanobelt S to ligand.
These results impel us to further design and synthesize a more
stable complex to withstand alkaline environments by using the
suited metal ions and by improving the ligand dispersibility in
H2O by functional modification, as a result to obtain a new
fluorescence probe to detect H2S in vivo.
Author Contributions
#K.L. and Z.L. contributed equally to this work.The manuscript
was written through contributions of all authors. All authors
have given approval to the final version of the manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We acknowledge the support from the National Natural
Science Foundation of China (21971257) and the Hunan
Provincial Science and Technology Plan Project of China
(2019TP1001). Y.-T.C. acknowledges the support from the
Ministry of Science and Technology of Taiwan (MOST106-
2628M-002-007MY3). The authors gratefully acknowledge the
NMR spectroscopy measurements from the Modern Analysis
and Testing Center of CSU.
ASSOCIATED CONTENT
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Detailed synthetic protocols and characterization data
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AUTHOR INFORMATION
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Pingshan Wang − Department of Organic and Polymer
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Interface Science, College of Chemistry and Chemical
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Die Liu − Institute of Environmental Research at Greater Bay
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Authors
Kaixiu Li − Department of Organic and Polymer Chemistry;
Hunan Key Laboratory of Micro & Nano Materials Interface
Science, College of Chemistry and Chemical Engineering, Central
South University, Changsha, Hunan 410083, China
Zhengguang Li − Department of Organic and Polymer
Chemistry; Hunan Key Laboratory of Micro & Nano Materials
Interface Science, College of Chemistry and Chemical
Engineering, Central South University, Changsha, Hunan
410083, China
Mingzhao Chen − Institute of Environmental Research at
Greater Bay Area; Key Laboratory for Water Quality and
Conservation of the Pearl River Delta, Ministry of Education;
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Guangzhou University, Guangzhou 510006, China
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