Multiaddressing Fluorescence Switch Based on a New

Article pubs.acs.org/JPCC

Multiaddressing Fluorescence Switch Based on a New Photochromic Diarylethene with a Triazole-Linked Rhodamine B Unit Shouzhi Pu,* Haichang Ding, Gang Liu, Chunhong Zheng, and Hongyan Xu Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang 330013, P. R. China S Supporting Information *

ABSTRACT: A novel diarylethene with a triazole-linked rhodamine B unit has been synthesized by click chemistry. When triggered by light, proton, and metal ions, the diarylethene can be used as a fluorescence switch, leading to a multiaddressable system. The diarylethene shows sequencedependent responses through efficient interaction of the specific triazole-linked rhodamine B unit with proton and metal ions. Furthermore, the diarylethene can serve as a nakedeye chemosensor for highly selective recognition of different metal ions in different solvent systems. The diarylethene was highly selective toward Al3+ with remarkable fluorescence change from dark to yellow in acetonitrile, while it selectively recognized Cu2+ with significant fluorescence change from dark to bright yellow in the mixture of acetonitrile and water (v/v = 4/6). Finally, a logic circuit was constructed with the unimolecular platform by using the combinational stimuli of light and chemical species as inputs and the fluorescence intensity at 595 nm as output.

1. INTRODUCTION Fluorescence signaling is a privileged approach for the detection of trivial amounts of chemical substances due to the high detection sensitivity and simplicity.1,2 Different external stimuli, including chemicals, electrons (or holes), and photons, can induce substantial changes to the spectral shape and/or peak intensity.3 Numerous fluorescence-based analytical methods have been developed and widely utilized in environmental chemistry and biological science.4−6 Thus, the regulation of fluorescent molecules has attracted much attention due to their potential applications in the development of sensors,7 switches,8 high density optical data storage,9 and logic gates.10 In particular, molecular fluorescence sensors and switches have been the central focus of recent studies,11−14 in which suitable fluorescent indicators were crucial due to their prompt response to external stimuli and distinctive changes in fluorescent spectra.15 Among the reported indicators, rhodamine derivatives are recognized as the most promising candidates for their excellent optical-physical properties, such as long wavelength absorption and emission, high fluorescent quantum yield, large extinction coefficient, and high stability against light.16,17 In general, rhodamine derivatives with spirocyclic structure are generally colorless and nonfluorescent. However, when their spirocyclic forms are stimulated by proton or metal ions, the open-ring forms turn into pink color with strong fluorescence.18−20 Therefore, rhodamine-containing compounds are typically utilized for naked-eye chemosensors.21 © 2014 American Chemical Society

So far, several successful attempts have been made to develop rhodamine-based molecular sensors for selective detection of metal ions such as Hg2+,22−25 Cu2+,22,26−30 Al3+,31 Fe3+,22,32−34 and Cr3+.22,35 For several decades, diarylethenes have been extensively investigated as one of the most promising photochromic molecules.36 They can be potentially applied in various optoelectronic devices due to their unique merits, such as remarkable fatigue resistance, excellent thermal stability, high sensitivity, and rapid response.37−40 It has been well documented that a reversible transformation between their open-ring and closed-ring isomers could be easily controlled by photoirradiation. Because the absorption spectra of the two isomers are distinctively different, they can be individually employed to represent ‘0’ and ‘1’ for a digital code in molecule switches.41 One possible way to achieve a fluorescence switch is to introduce a fluorescent chromophore into diarylethene structures.42−45 Recently, some fluorescence switches based on diarylethenes have been reported.46−50 For instance, Tian and co-workers reported a new multistate 1,8-naphthalimidepiperazine-tethered dithienylethene molecule with fluorescence tunable by Cu2+, proton, and light.46 Zheng et al. reported a dual-controlled switching molecule using rhodamine as a donor Received: January 7, 2014 Revised: February 27, 2014 Published: March 7, 2014 7010

dx.doi.org/10.1021/jp5001495 | J. Phys. Chem. C 2014, 118, 7010−7017

The Journal of Physical Chemistry C

Article

Scheme 1. Photochromism of Diarylethene 1 by Light

Scheme 2. Synthesis Route to Diarylethene 1O

fluorophore and the closed-ring form of diarylethene as an acceptor.47 Previously, we reported a fluorescence switch based on a diarylethene with a rhodamine unit, which showed good fluorescent modulation and naked eye recognition properties to metal ions.39 However, the reported derivatives can only recognize certain metal ions in a single solvent system, and their fluorescent modulation efficiency and selectivity need to be further enhanced. It is still a challenge to develop new diarylethenes that can selectively recognize different metal ions in different solvent systems. In this work, a new diarylethene with a triazole-linked rhodamine B unit (1O) was synthesized by click chemistry (Scheme 1). The diarylethene afforded a dual-controlled switch because its fluorescence was well controlled by both protons and light stimuli. Furthermore, it is interesting that the compound also served as a naked-eye chemical sensor for highly selective recognition of different metal ions in specific solvent systems. When 1O bound Al3+ in acetonitrile, the emission intensity of the binding complex was enhanced with notable fluorescence change from dark to yellow. In contrast, when 1O bound Cu2+ in the mixture of acetonitrile and water (v/v = 4/6), its emission intensity increased significantly with fluorescence change from dark to bright yellow. To the best of our knowledge, our experimental results provided the first example of solvent system-based highly selective metal ion recognition.

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C NMR spectra were collected on a Bruker AV400 (400 MHz) spectrometer with CDCl 3 as the solvent and tetramethylsilane (TMS) as an internal standard. Melting point was measured using a WRS-1B melting point apparatus. Mass spectra were obtained on an Agilent 1100 ion trap MSD spectrometer. Elemental analysis was carried out with a PE CHN 2400 analyzer. UV−vis spectra were measured on an Agilent 8453 UV/vis spectrophotometer. Fluorescence spectra were recorded with a Hitachi F-4600 fluorescence spectrophotometer. Infrared spectra (IR) were collected on a Bruker Vertex-70 spectrometer. Photoirradiation experiments were performed using an SHG-200 UV lamp, Cx-21 ultraviolet fluorescence analysis cabinet, and a BMH-250 visible lamp. 2.2. Synthesis of the Target Compound. The synthetic route for 1O is shown in Scheme 2. Precursor 2 was synthesized by the reported method.51 First, 2 was reduced to 3 by NaBH4 in THF. Reacting 3 with DBU and DPPA in THF gave the azide 4. Then, compound 6 was prepared by reacted 5 with N2H4·H2O in methanol, and it was further treated with propargyl bromide in the presence of K2CO3 in CH3CN at 85 °C to give 7. Finally, the target diarylethene, 1(2-methyl-3-benzothiophenyl)-2-{2-methyl-5-[4-(rhodamine B hydrazyl-methyl-(1,2,3-triazole))tolyl]-3-thienyl}perfluorocyclopentene (1O), was obtained by click reaction between by compounds 4 and 7. The detailed experimental procedures and data are summarized in the Supporting Information.

2. EXPERIMENTAL SECTION 2.1. General Methods. All solvents used were of spectrograde and purified by distillation prior to use. Expect for Mn2+, K+, and Ba2+ (their counterions were chloride ions), other metal ions were obtained by the dissolution of their respective metal nitrates (0.1 mmol) in distilled water (10 mL). 1H and

3. RESULTS AND DISCUSSION 3.1. Photochromism. The photochromic behavior of 1O was examined in CH3CN solution at room temperature, and its absorption spectral and color changes induced by alternating irradiation with UV light (297 nm) and visible light (λ > 500 7011



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Figure 1. Absorption and emission spectral changes of 1O in acetonitrile solution after the addition of 100 equiv TFA: (A) absorption spectral change and (B) emission spectral change, excited at 520 nm.

Figure 2. Absorption and emission spectra changes of 1O′ in acetonitrile upon alternating irradiation with UV/vis light: (A) absorption spectral change and (B) emission spectral change.

formation of the open-ring amide form of rhodamine B, corresponding to solution color change from colorless to pink (Figure 1A). Simultaneously, the fluorescence at 595 nm was significantly enhanced with a color change from dark to bright yellow after the addition of 100 equiv of TFA, which could be easily observed with the naked eyes (Figure 1B). Initially, the acetonitrile solution of 1O was nonfluorescent with excitation at 520 nm but became increasingly fluorescent after adding TFA due to the formation of an open-ring fluorescent rhodamine moiety. As the fluorescence intensity at 595 nm reached the maximum, the fluorescent quantum yield of the protonated solution of 1O (1O′) was determined to be 0.55 with rhodamine B as a reference. The gradual back addition of the equal amount of TEA regenerates the spirolactam form of rhodamine, while the fluorescent intensity decreased to the original state. The quenching by the addition of TEA returned the pink solution to colorless. Furthermore, diarylethene 1O′ also underwent photoisomerization by light irradiation. The absorption and fluorescence spectra of 1O′ in acetonitrile by light irradiation are shown in Figure 2. Upon irradiation at 297 nm UV light, the pink solution of 1O′ turned purple with the concomitant appearance of new visible absorption band centered at 558 nm due to the formation of the closed-ring isomer 1C′ (Figure 2A). The visible absorption band became broader and stronger because of an overlap between the closed-ring diarylethene and rhodamine. The purple color and the absorption spectrum

nm) are shown in Figure S1, Supporting Information. Generally, the diarylethene should undergo a photoisomerization reaction by photoirradiation. As expected, upon irradiation at 297 nm UV light, the colorless solution of diarylethene 1O turned purple and a new absorption band centered at 550 nm emerged due to the formation of the closed-ring isomer 1C with larger π-electron delocalization in the molecule.52 The colored solution of 1C was bleached entirely upon irradiation with visible light (λ > 500 nm), and its absorption spectrum returned to its initial state. The reversibility of spectral changes originated from the reversible structural transformation between isomers 1O and 1C. After 10 repeat cycles, no remarkable decomposition was detected by UV/vis spectral analysis. When arrived at the photostationary state, the photoconversion ratio from the open-ring to the closed-ring isomer determined by HPLC analysis was 91%. The cyclization and cycloreversion quantum yield of the diarylethene were 0.48 and 0.04, respectively. 3.2. Dual-Fluorescence Switching Property by Proton and Photon Stimuli. It is well-known that the open-ring form of rhodamine moiety emits strong fluorescence within the range of 540−700 nm in the presence of metal ions or proton.18,53 The room temperature absorption and emission spectra of diarylethene 1O in acetonitrile with gradual addition of TFA are shown in Figure 1. When 100 equiv of TFA were added into the acetonitrile solution of 1O, a new visible absorption band centered at 558 nm appeared because of the 7012



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Figure 3. Principle of dual-mode fluorescence switching and the color change for compound 1O.

Figure 4. Changes in the fluorescence of 1O induced by the addition of various metal ions (10 equiv) in acetonitrile (2.0 × 10−5 mol L−1): (A) emission spectral changes, (B) emission intensity changes, and (C) photographs of the color changes in solution and fluorescence.

isomer, which adequately restored the emission spectrum back to its original one. As mentioned above, the emission intensity of diarylethene 1O could be independently modulated by either chemical or optical stimuli, which could be employed as a dual fluorescent molecular switch. While the rhodamine motif served as energy transfer (ET) donor, the diarylethene motif served as ET acceptor.55 The principle of dual-mode fluorescence switching and the color change for compound 1O are illustrated in Figure 3. 3.3. Fluorescent Probe for Metal Ions in Different Solvent Systems. For the detection of metal ions, fluorescent sensors are advantageous because of operational simplicity, low detection limit, real-time detection, and high portability.56−61 Consequently, high-performance fluorescent probes have been

returned the original state upon irradiation with appropriate visible light. It is worth noting that the emission intensity at 595 nm decreased dramatically along with the photoisomerization from 1O′ and 1C′ upon exposure to UV light (297 nm). When arrived at the photostationary state, the emission intensity of 1C′ was quenched to only 17% of its initial value. It was proposed that the fluorescent quenching process involved an intramolecular fluorescence resonance energy transfer (FRET) mechanism. Because the emission band of rhodamine (550− 700 nm) at the open-ring state overlapped with the absorption band of the closed-ring isomer of diarylethene (450−650 nm), the desired FRET process could occur when fluorescent energy was transferred from the excited rhodamine amide unit (donor) to the diarylethene unit (acceptor).54 Subsequent irradiation with visible light (λ > 500 nm) regenerated the open-ring 7013



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Figure 5. Changes in the fluorescence of 1O induced by the addition of various metal ions (10 equiv) in acetonitrile/water solvent (v/v = 4/6): (A) emission spectral changes, (B) emission intensity changes, and (C) photographs of the color changes in solution and fluorescence.

coordination to Al3+ or Cr3+, thereby diminishing the fluorescence response of 1O.63,64 However, a notable enhancement in fluorescence intensity at 595 nm was observed for 1O when 10 equiv of Cu2+ was added. Meanwhile, the solution was changed from colorless to pink, accompanied by the fluorescence color change from dark to bright yellow. In acetonitrile/water (v/v = 4/6), almost no changes in fluorescence of 1O was observed with any of the other metal ions mentioned above. The results indicated that 1O was highly selective toward Cu2+ over other competing cations in acetonitrile/water binary solvent system. In order to confirm the unique selectivity of 1O as a chemosensor for Cu2+ in acetonitrile/water binary solvent, competitive experiments were performed in the presence of a wide range of metal ions, such as Al3+, Cr3+, Co2+, Ni2+, Mn2+, Hg2+, Pb2+, Cd2+, Zn2+, K+, Ca2+, Mg2+, Ba2+, and Sr2+. As shown in Figure 6, no obvious interference in its fluorescence was observed when Cu2+ (10 equiv) added with most other metal ions (25 equiv) except Al3+ and Cr3+. No significant variation in emission intensity was found in comparison with that containing Cu2+ alone. The result indicated that 1O could be served as an efficient and selective fluorescent chemosensor for recognition of Cu2+ even competing with other related species in acetonitrile/water binary solvent (v/v = 4/6). In order to further elucidate the interference of Al3+ and Cr3+, Figure 7 shows the emission intensity of 1O as a function of time in the presence of 10 equiv of Cu2+ in acetonitrile/water binary solvent system. In the presence of Cu2+, an increase in emission intensity at 595 nm was observed for 1O. When arrived at the plateau state, a 223-fold fluorescence enhancement was achieved after 10 min. In contrast, only about an 11fold fluorescence enhancement was achieved after Al3+ or Cr3+ was added into the solution for 45 min. These results suggested that the interference of Al3+ or Cr3+ was negligible during the course of Cu2+ detection.

developed in numerous applications in various multidisciplinary research.16,62 In the present work, diarylethene 1O was identified as an outstanding fluorescent chemosensor for the detection of specific metal ions. It could serve as a naked-eye chemical sensor for both Al3+ and Cr3+ in acetonitrile and highly selective recognition of Cu2+ in aqueous acetonitrile (v/v = 4/6). Figure 4 showed the emission spectrum of 1O, and its intensity at 595 nm changes in acetonitrile (2.0 × 10−5 mol L−1) induced by the addition of various metal ions (10 equiv), such as Al3+, Cr3+, Cu2+, Co2+, Mn2+, Ni2+, Hg2+, Pb2+, Zn2+, Cd2+, K+, Ca2+, Mg2+, Ba2+, and Sr2+, when excited at 520 nm. It could be easily seen that the fluorescence intensity of 1O was enhanced approximately 450-fold with notable fluorescent color change from dark to yellow when Al3+ was added. It is noteworthy that the addition of Cr3+ also resulted in fluorescence enhances of 1O, but the fluorescence intensity of the 1O−Cr3+ complex was only about half of that of 1O− Al3+ complex, and its fluorescence color changed from dark to light yellow (Figure 4A,C). When Cu2+ was added into the acetonitrile solution of 1O, the solution changed from colorless to pink, but its emission intensity did not show much increase. The stimulation of other metal ions, including Co2+, Mn2+, Ni2+, Hg2+, Pb2+, Zn2+, Cd2+, K+, Ca2+, Mg2+, Ba2+, and Sr2+, induced almost no changes in the emission intensity of 1O in acetonitrile (Figure 4B). Consequently, only Al3+ significantly changed the fluorescence of 1O in acetonitrile, indicating that the diarylethene was selective toward Al3+ over other metal ions in acetonitrile, except Cr3+. Furthermore, the changes in the fluorescence of 1O induced by different metal ions were also investigated in acetonitrile/ water binary solvent system (v/v = 4/6) at room temperature, and the result is shown in Figure 5. It is surprising that the response of 1O to Al3+ or Cr3+ was dramatically suppressed by water in the binary solvent system. This may possibly be ascribed to the competition of water molecules with 1O for 7014



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was completely quenched. As a result, the output signal was ‘off’ and the output digit was ‘0’. All of the possible logic strings of the three inputs are listed in Table 1, and the combinational logic circuits equivalent to the truth table is shown in Figure 8. Table 1. Truth Table for All Possible Strings of Three Binary-Input Data and the Corresponding Output Digit outputa

input

Figure 6. Competitive tests for the fluorescence responses of 1O to various metal ions in acetonitrile/water binary solvent (v/v = 4/6). Bars represent the ratio of emission intensity at 595 nm. Red bars represent the addition of 25 equiv of various metal ions to the solution of 1O. Gray bars represent the addition of Cu2+ (10 equiv) to the above solution, respectively.

In1 (UV)

In2 (vis)

In3 (TEA)

λem = 595 nm

0 1 0 0 1 1 0 1

0 0 1 0 1 0 1 1

0 0 0 1 0 1 1 1

1 0 1 0 1 0 0 0

a

At 595 nm, the emission intensity below 50% of the original value is defined as 0, otherwise defined as 1.

Figure 8. Combinational logic circuits equivalent to the truth table given in Table 1: In1 (297 nm UV light), In2 (500 nm visible light), In3 (TEA), and output (in acidic condition). Figure 7. Changes in emission intensity of 1O with time in the presence of Cu2+ in acetonitrile/water binary solvent (v/v = 4/6). Inset shows the emission intensity changes of 1O at 596 nm as a function of time (0−45 min).

4. CONCLUSIONS A novel diarylethene has been designed and synthesized by connecting rhodamine B as a fluorophore and perfluorodiarylethene as a photoswitching unit via a triazole linkage. The fluorescence of the diarylethene could be effectively triggered by light and chemical stimuli. On the basis of this characteristic, a dual-control switch and an integrated digital circuit have been successfully designed and constructed. Moreover, the target compound exhibited high selectivity for the detection of specific metal ions in different solvent systems, and the diarylethene could be used as a naked-eye fluorescent chemosensor. The results are helpful for constructing new photochromic diarylethenes with multiaddressable fluorescence switching properties and metal ion recognition capabilities.

3.4. Application in Logic Circuit. On the basis of the fact that the fluorescence intensity of 1O could be effectively modulated by light and proton, a combinational logic circuit was constructed by three input signals (ultraviolet stimulus, visible light stimulus, and TEA stimulus) and an output signal (fluorescent intensity at 595 nm). The three input signals were represented by In1, In2, and In3, respectively, and they could be either ‘on’ state or ‘off’ state with different Boolean values. For instance, when UV irradiation (297 nm) was employed, input signal In1 was switched to ‘on’ state with a Boolean value ‘1’. Similarly, input signal In2 was ‘1’ when visible light was used, and In3 was ‘1’ when TEA was added. Under the acidic condition, 1O exhibited strong fluorescence, and then its intensity was employed as an initial state. The output signal could be regarded as ‘off’ when the emission intensity at 595 nm was below 50% of the original value; otherwise, the output signal was regarded as ‘on’. The binary digits (‘0’ and ‘1’) can be used instead of the two levels (‘off’ and ‘on’). Consequently, the diarylethene 1 can read a string of three inputs and write one output. For example, when the string is ‘0, 0, and 1’ its corresponding input signals In1, In2, and In3 are ‘off, off, and on’, respectively. Under these conditions, compound 1O′ was converted to 1O by the stimulation of TEA and its fluorescence

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ASSOCIATED CONTENT

S Supporting Information *

Details of experiments, characterization data for all compounds, and absorption spectra of the target diarylethene in hexane. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. 7015



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The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors are grateful for the financial support from the National Natural Science Foundation of China (21262015, 21362013, and 51373072), the Project of Jiangxi Advantage Sci-Tech Innovative Team (20113BCB24023), the Science Funds of Natural Science Foundation of Jiangxi Province (20122BAB213004 and 20132BAB203005), and the Project of the Science Funds of Jiangxi Education Office (KJLD12035 and GJJ12587).

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