A fluorescent sensor for detection of grinding force and fluoride ion based on acylhydrazone derivative

Journal Pre-proof A fluorescent sensor for detection of grinding force and fluoride ion based on acylhydrazone derivative Xingyu Zheng, Binglian Bai, Zhiming Li, Jue Wei, Haitao Wang, Min Li, Hong Xin PII:

S0143-7208(19)32251-X

DOI:

https://doi.org/10.1016/j.dyepig.2019.108153

Reference:

DYPI 108153

To appear in:

Dyes and Pigments

Received Date: 20 September 2019 Revised Date:

7 December 2019

Accepted Date: 17 December 2019

Please cite this article as: Zheng X, Bai B, Li Z, Wei J, Wang H, Li M, Xin H, A fluorescent sensor for detection of grinding force and fluoride ion based on acylhydrazone derivative, Dyes and Pigments (2020), doi: https://doi.org/10.1016/j.dyepig.2019.108153. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier Ltd.

Xingyu Zheng: Software,writing, Data Curation Binglian Bai: Investigation, Resources, Methodology, Project administration. Zhiming Li: Software. Jue Wei: Formal analysis. Haitao Wang: Supervision Min Li: Funding acquisition Hong Xin: Software

The AIE-active PSD exhibits high sensitivity toward F− anion and grinding/heating stimulated fluorescence switching property.

A fluorescent sensor for detection of grinding force and fluoride ion based on acylhydrazone derivative Xingyu Zheng a, Binglian Bai*a, Zhiming Li a, Jue Wei*a, Haitao Wang b, Min Li *b and Hong Xin c a

College of Physics, Jilin University, Changchun 130012, PR China. E-mail:

[email protected], [email protected]; b Key Laboratory for Automobile Materials, Ministry of Education, Institute of Materials Science and Engineering, Jilin University, Changchun 130012, PR China. E-mail: [email protected]; C School of Chemistry and Chemical Engineering, Shenzhen University, Shenzhen 518060, PR China.

Abstract: A new AIE-active pyrene-substituted acylhydrazone derivative (PSD) with multi-stimuli-responsive fluorescence switching behaviors has been designed and synthesized. The PSD exhibits the unusual AIE property and mechanofluorochromism (MFC) behavior with emission colors reversibly changing from blue-green to yellowish-green upon grinding and annealing. The MFC properties might be attributed to the synergetic effect of the different pyrene excimers formation and the crystalline-amorphous

phase

transition.

Simultaneously,

the

PSD

exhibited

high-contrast fluorescent switching properties with high selectivity to F−. In the presence of F−, the PSD in DMSO dilute solution fluorescence quenched, and visible color changed from transparent to orange by the naked eye. The binding constant of PSD-F−complex calculated from the Benesi-Hildebrand plot was 5.08×103 M−1 and the detection limit for sensing F− in DMSO solution was 0.159 µM. Keywords: Acylhydrazone, Stimuli responsive, Aggregation induced emission (AIE), Mechanofluorochromism, F− detection 1. Introduction The stimuli-responsive luminescent materials have gained considerable attention because their physical or chemical properties can change with respect to external stimuli, such as heat, light, electrical, ion, and force [1-5]. Mechanofluorochromic (MFC) materials have recently been developed rapidly in that the fundamental

relevance of their molecular structures and the properties and the prospect for application in sensors, light devices, security inks, and optical information storage [6-10]. Nowadays, abundant organic MFC compounds have been developed [11-26]. However, the reports of the MFC behaviours of the acylhydrazone derivative are still limited. Recently, we synthesized some acylhydrazone derivatives substituted by alkoxy and confirmed that they showed obviously MFC behaviours [27-30]. Simultaneously, Sarma et al. [31] reported that the MFC behaviours of the acylhydrazone derivatives AI (substituted by pyridine group) and AB (substituted by benzene group) exhibited obvious difference and the introduction of pyridine heteroatom is very important. For example, AI exhibited yellow-green emission after grinding, which could be easily switched “off”’ when was exposed to N,N-dimethylformamide, whereas AB did not exhibit MFC behaviour under the same conditions. Based on these findings, the thiophene heteroatom was introduced to develop new MFC materials as well as obtain a better understanding of the relationship between structure and property. The detection of environmental and biological anions has significant effects on human health and the environment. Therefore, design and development of sensing and recognition for different anions have grown into an area of great interest in recent years [32-39]. Among various anions, fluoride plays significant roles in chemical, environmental and biochemical process. A great many of compounds have been synthesized to detect the F− [40-45]. Recently, the compounds with multi-stimuli-responsive properties have gained more and more attention because they are more efficient compared with sensors for a single

target

[46-48].

However,

the

compounds

with

MFC

and

F−

dual-stimuli-responsive properties are still limited [49]. In this study, we focus on the synthesis and study a new fluorescent compound, 2-thiophene-1-pyraniazide (PSD), which exhibits obvious aggregation-induced emission enhancement effect and MFC properties. In addition, the PSD shows excellent highly selective F− sensing.

N

S

H N O

PSD Scheme 1. The molecular structure of PSD 2. Experimental section

The synthetic route of PSD was shown in Scheme S1. The compound 2-thiophene-1-pyraniazide (PSD) was synthesized by 1.42g of 2-Thiophenecarboxylic acid hydrazide (0.01mol) reacting with 1-Pyrenecarboxaldehyde (2.53g, 0.01mol) in ethanol (150mL) under reflux condition for 8 h. The crude product was isolated and purified by recrystallization from THF for further 1H NMR, 13C NMR (Fig. S1), MS (Fig. S2), FT-IR measurements and elemental analysis experiments. The melt point of PSD is 273℃. 1

H NMR (300 MHz, DMSO-d6), (ppm, from TMS): 12.10-12.01 (d, 1H), 9.50-9.28 (d,

1H), 8.84-8.73 (m, 1H), 8.60-8.52(m, 1H), 8.40-8.36 (m, 4H), 8.30-8.22 (d, 2H), 8.20-8.10 (m, 1H), 8.08-7.84 (d, 2H), 7.31-7.28 (m, 1H). 13

C NMR (75 MHz, DMSO-d6), (ppm, from TMS): 146.28, 142.18, 135.00, 131.91,

130.86, 130.13, 128.73, 128.43, 127.40, 126.84, 126.64, 126.13, 125.81, 125.33, 124.11, 123.77, 122.42, 121.71. FT-IR (silicon pellet, cm-1): 3358, 3167, 3034, 2920, 2848, 1637, 1597, 1412, 1384, 1326, 1107, 842, 704, 606. Elemental analysis: calculated for C22H14N2OS: C, 74.55; H, 3.98; N, 7.90; S, 9.05. Found: C, 74.97; H, 4.053; N, 7.89; S, 9.21. MS: calcd for C22H14N2OS: 354.08, found: 355.09. Single-Crystal XRD data of PSD crystal: Monoclinic, space group P21/C, a=13.6544(4) Å, b=9.9969(3) Å, c=12.6004(4) Å, α=90°, β=99.6210(1)°, γ=90°, d=1.338g/cm3, V=1695.78(9) Å3, Z=4, T=293 K, total reflections=26415, unique reflections=4221,

R(int)=0.0258,

GOF=1.062,

Final

wR2=0.1998, R indices (all data) R1=0.0612, wR2=0.1825.

R

indices

R1=0.0750,

3. Results and discussion 3.1. Aggregation-induced emission (AIE)

Fig. 1 (a) Fluorescence spectra of PSD in THF/water solution with different volume

fraction of water (1×10-5 M, λex = 380 nm); (b) A plot of maximum PL intensity versus water volume fractions; (c) Fluorescent photographs of PSD in THF/water solutions with different volume fraction of water.

Fig. 2 SEM images of PSD in THF-H2O mixtures with (a) 0% and (b) 90% water

volume fractions. To explore whether compound PSD has an aggregation-induced emission (AIE)

property, the UV-Vis and emission behaviors in THF-water solutions with different volume fractions of water added were studied. On account of the poor solubility of PSD in water, the phenomenon of molecular aggregation could occur in the context of

increasing the volume fraction of water in THF/ H2O mixtures, and thereby their UV and fluorescence spectra were changed. As shown in Fig. 1, it can be seen that PSD shows two weak emission peaks at 414 nm and 436 nm in THF dilute solution and exhibits a blue fluorescence. The emission intensity of PSD was steadily increased, accompanied by a slight red shift of the maximum emission peak as the water content less than 60 %, which may be due to the restricting intramolecular rotations caused by the formation of molecular aggregates. And the absorption spectra band is slightly widened and the SEM morphology exhibit irregular aggregation in this region (Fig. S3, S4). Nevertheless, the emission intensity decreases sharply when the water content is increased to 80% and a new shoulder emission peak appeared at 457 nm. When the water content reaches 90%, the maximum emission peak has a large red shift (shift to 513 nm), emission color changed into yellow-green. Meanwhile, the absorption spectra of PSD (Fig. S3) also has a big red shift and there is a long tail in the visible region, and the SEM morphology exhibits long fibrous aggregation (Fig. 2). Based on the above results, the unusual AIE phenomenon of PSD can be assumed as follows: The PSD single molecule is likely torsional conformation in dilute solution, which is supported by the potential energy curve of the theoretical simulation (Fig. S6), so PSD exhibits a blue fluorescence in THF dilute solution should be attribute to the fluorescence emission of pyrene chromophore. When the water fractions are between 10% and 70 %, the molecular aggregates restrict intramolecular rotations, the fluorescence changes show the common AIE phenomenon with a blue emission. Meanwhile, the viscosity-dependent and temperature-dependent of fluorescence experiments can further support that this common AIE behavior is due to the restricting the internal rotation of the single molecule. It can be seen from Fig. S7 and Fig. S8 that the fluorescent intensities increase with the increasing of the solvent viscosity or the decreasing of the

temperature [50]. The state with 80% water volume fraction is a transition state, and the SEM morphology exhibits that there is a tendency to form fibers (Fig. S4), which demonstrates the self-assembly began to be driven by directional intermolecular interactions [51]. When the water fractions reach to 90 %, the intermolecular interaction is further strengthened, and the molecules further self-assembly to form fibers under the strong intermolecular interactions, mainly is intermolecular hydrogen bonding between C=O and –NH groups and π-π interactions among pyrenyl groups. It is likely that the molecules show conformational planarization due to the self-assembly under strong directional intermolecular interaction in a fiber, and the conformational planarization is also supported by the results of single crystal and the theoretical simulation (Fig. S5 and Fig. S6). The aggregation-induced planarization extends the effective conjugation length. Simultaneously, the strong interactions decrease the intermolecular distance (It can be supported by the decrease of the d-spacing of the fibers (Fig. S9).), thus the nonradiative decay increases, and the fluorescent intensity decreases greatly [52]. In addition, the strong π-π interactions are also in favor of the formation of pyrene excimers in fibers. So the color change of fluorescence emission is attributed to the synergetic effect of conformational planarization and the pyrene excimers formation in fibers. 3.2. Mechanofluorochromic behavior of PSD

The single crystals (quantum yield ΦF=1.27%) of PSD were successfully obtained through a slow evaporation process in THF solutions at room temperature. The detailed crystallographic data of PSD are summarized in experimental section. As shown in Fig. 3 and Fig. S10, it is evident that the pyrenyl ring and the thiophene ring are nearly planarization with the dihedral angle (φ) found to be 8.39°. The distance of nearest neighbour pyrenyl ring is about 3.368 Å, and the slip distance of the adjacent pyrenyl ring along the long axis of molecules (∆y) is 1.361 Å and 1.847 Å along the short axis (∆x), which indicates that the intermolecular contact between pyrenyl groups is the strong π-π stacking. The two PSD molecules reversed arrange to form dimer through strong intermolecular hydrogen bonding between

-C=O and H-N- (hydrogen bond length 2.099Å), and then self-assembled along b axis through strong π-π stacking between neighbouring pyrene planes to form supramolecular aggregates. In addition, the molecule self-assembled by a zigzag layer packing along c axis in view on a axis (Fig. S11).

Fig. 3. (a) The top view of the adjacent pyrene ring along the π-stacking direction in PSD crystals, (b) the intermolecular hydrogen bonding interactions.

Fig. 4 (a) Fluorescence images and (b) Fluorescent emission spectra of PSD under

external stimuli: pristine, grind and anneal at 110 ℃ for 20 min (λex = 400 nm).

It can be seen from Fig. 4 that the PSD pristine powder showed blue-green emission at 484 nm (quantum yield ΦF=12.03% and the average lifetime [τ]= 1.59 ns). As a result of grinding, the blue-green emission transformed to a yellowish-green fluorescence with the corresponding emission maximum shifting from 484 to 524 nm (quantum yield ΦF=17.59% and the average lifetime [τ]= 8.98 ns), and the intensity of the fluorescence almost unchanged, which is similar to that of single crystal before and after grinding (Fig. S13). It can be found that both the quantum yield and average lifetime of ground sample increase, compared with the pristine powder. Thus, the emission at 524 for ground sample probably originate from completely overlapping pyrenyl excimer [53], which is also supported by the big blue shift in the absorption spectra of ground sample, compared with the pristine powder (Fig. S15). The ground sample cannot spontaneously recover to the original state under room temperature without the exertion of any external stimulation, whereas the ground sample could convert into its original state under treatment with annealing the ground sample at 110 ℃ for 20 min, which indicated that the reversible MFC behavior could be achieved. However, the mechanochromic property cannot be completely recovered by fuming with THF solvent (Fig. S16). Furthermore, the scanning electron microscopy (SEM) was employed to observe the change of morphology. As shown in Fig. S17, the lumpy crystals were observed for the PSD pristine powder, whereas the ground samples exhibited random distribution. After treated by annealing, the lumpy crystals can be restored. The XRD experiment is a useful tool to further investigate the relationship between the structure and property. We conducted the XRD experiments of PSD and the results were shown in Fig. 5. There are five strong peaks with the d-spacings of 13.49 Å, 6.68 Å, 5.37 Å, 4.47 Å, and 3.89 Å for PSD pristine powder, implying the formation of an ordered crystalline structure. The ground PSD sample showed that the sharp peaks nearly disappeared, indicating that the PSD has experienced a disruption process from well-ordered crystalline structure to amorphous phase under the condition of grinding. There is a relatively strong diffraction peak appeared at 2θ=28° (d=3.18 Å) in the XRD pattern after grinding, indicating the increase in π-π

interaction [54]. However, almost all the reflection signals were recovered in the annealed sample, which indicates that the color change of fluorescence emission is attributed to the crystalline-amorphous phase transition and is reversible by treating with grinding and annealing (or recrystallizing from THF (Fig. S18)). The DSC experiments (Fig. S19) show that the melting points (273℃) of PSD before and after grinding are same, but PSD after grinding exhibited a clearly exothermic peak at 105 ℃, which was correlated with the cold-crystallization of ground sample, indicating that the ground sample was in an unstable amorphous state and could be transformed into a stable state through the process of cold-crystallization. So the color change of fluorescence emission before and after grinding is attributed to the synergetic effect of the different pyrene excimers and the crystalline-amorphous phase transition.

Fig. 5 The XRD patterns of PSD in solid states. 3.3. Anion responsive properties

Fig. 6 (a) Absorption (b) emission spectra of PSD in the presence of various anions

(16 equiv.) in DMSO solution (5×10-5 M) and (c) Photos (under daylight and UV light) of PSD solution before and after addition of F− (20 equiv.). The F− sensing property of PSD is studied in DMSO solution. After addition of 20 equiv. TBAF, the solution shows a noticeable color change from colorless to orange and the blue fluorescence emission disappears (Fig. 6). To investigate the interactions of receptor PSD with anions, the UV–Vis absorption spectra were done after adding TBA salts of F−, Cl−, Br−, AcO− and H2PO4− to its DMSO solution. As shown in Fig. 6, when 16 equiv. of F− was added, the maximum absorption band at 379 nm decreased and a new absorption band centered at 454 nm appeared. Nevertheless, other anions (Cl−, Br−, AcO− and H2PO4−) did not bring about any significant signal response, indicating no interactions with PSD. Since there is a broad band in the visible area, the addition of F− can lead to a significant change in color. The interaction of PSD with F− was further confirmed by the fluorescence spectra changes upon addition of TBA salts of F−, Cl−, Br−, AcO− and H2PO4− to its DMSO solution (Fig. 6). Apparently, only F− induced the emission red-shift and almost disappearance, whereas the fluorescence intensity only slightly changed after adding

the other tested anions. In order to reveal the sensing mechanism, the fluorescence and UV-Vis absorption spectra titration experiments were performed (Fig. S20 and Fig. S21). On addition of F−, the absorption band located at 379 nm of PSD decreased and redshifted step by step, and a new absorption peak at about 454 nm appeared and increased. Meanwhile, the fluorescence intensity gradually decreased and has a slightly red-shift upon addition of F−, and the emission bands unchanged through the adding of 7 equiv. of F− (Fig. S21). To better study the interaction of F− with the compounds, the calculation of the association constant Ka was performed. The Benesi–Hildebrand method, which is the most commonly used method, could be used for determining association constants based on absorbance spectra. We plotted (Amax−Amin) / (A−Amin) against 1/[F−] (as shown in Fig. S22) [55,56], it indicated that PSD and fluorine ions form 1:1 complexation, and the association constant Ka was 5.08 × 103 M−1. The detection limit for sensing F− in DMSO solution was 0.159 µM, which was obtained from the plot of absorption as a function of F− concentration (Fig. S23 and S24) [57]. The red-shift of absorption and the emission spectral may be caused by the extended conjugate system formed by the deprotonation reaction. In order to deeper look into the reaction mechanism of PSD to F−, we carried out 1H NMR titration experiments in DMSO-d6 (Fig. S25). It was easy to find that the signal of N-H proton at about 12.09 ppm disappeared completely after the addition of F−, and the aromatic proton signals shifted upfield, indicating that the N-H group underwent a deprotonation reaction [58-60]. The proposed reaction mechanism of the PSD with fluoride was shown in Scheme S2. To determine the practical applications of PSD towards F−, competitive experiments were performed with 10 equiv. of F− and 10 equiv. of other anions (Cl−, Br−, AcO−, H2PO4−) in DMSO solution (Fig. S26). The absorption/emission spectra of PSD with F− were not influenced by the subsequent addition of competing anions. 4. Conclusion

In summary, we designed and synthesized thiophene substituted pyrene acylhydrazone derivative, the 2-thiophene-1-pyraniazide (PSD). The PSD exhibits multiple fluorescence switching behaviors to external stimulus. Firstly, The PSD could exhibit fluorescence color conversion from blue to green as the unusual AIE property. The PSD could form different aggregates in THF/water solutions with different fractions of water addition, the formation of different aggregates caused obvious fluorescence changes. Secondly, the PSD exhibited reversible MFC with the emission colors changing from blue-green to yellow-green upon grinding. The MFC properties might be attributed to the synergetic effect of the different pyrene excimers formation and the crystalline-amorphous phase transition. Thirdly, The PSD exhibited remarkable fluorescence quenching and visible color changes in the presence of F− in DMSO dilute solution, respectively. After the addition of F−, the deprotonation reaction of amide(-N-H) group could form the extended conjugated system, which could be confirmed by absorption and 1H NMR experiments. And PSD can only selectively detect F− in the presence of other competitive anions. Acknowledgments

This work was supported by the Natural Science Foundation of Jilin Province (No.20170101112JC), the Project 985-Automotive Engineering of Jilin University and

the

Project

of

Science

and

Technology

Plan

of

Shenzhen

City

(No.JCYJ20180305125649693) . References

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1.

Pyrene-substituted acylhydrazone derivative (PSD) shows an unuaual

aggregation-induced emission phenomenon. 2.

The PSD exhibits mechanofluorochromism behavior with emission colors

reversibly changing upon grinding and annealing. 3.

The PSD shows high selectivity and sensitivity toward F− in DMSO solution.

Conflicts of interest

This article is no conflict to declare.