In Situ Control of Multicolor Luminescence over the Entire Visible Spectral Region in a Single Chromophore by Sol–Gel Transformation and Dynamic Metal–Ligand Coordination

Open AccessCCS ChemistryCOMMUNICATION1 Sep 2021In Situ Control of Multicolor Luminescence over the Entire Visible Spectral Region in a Single Chromophore by Sol–Gel Transformation and Dynamic Metal–Ligand Coordination Yun Ma, Fan Yu, Shujun Zhang, Pengfei She, Shujuan Liu, Wei Huang and Qiang Zhao Yun Ma Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 Google Scholar More articles by this author , Fan Yu Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 Google Scholar More articles by this author , Shujun Zhang Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 Google Scholar More articles by this author , Pengfei She Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 Google Scholar More articles by this author , Shujuan Liu Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 Google Scholar More articles by this author , Wei Huang *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 Frontiers Science Center for Flexible Electronics (FSCFE), MIIT Key Laboratory of Flexible Electronics (KLoFE), Shaanxi Key Laboratory of Flexible Electronics, Xi’an Key Laboratory of Flexible Electronics, Xi’an Key Laboratory of Biomedical Materials & Engineering, Xi’an Institute of Flexible Electronics, Institute of Flexible Electronics (IFE), Northwestern Polytechnical University, Xi’an 710072 Google Scholar More articles by this author and Qiang Zhao *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210023 Google Scholar More articles by this author https://doi.org/10.31635/ccschem.020.202000525 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Controlling multicolor luminescence in a single chromophore is of fundamental significance but remains a great challenge. In this study, a carbazole group was incorporated into terpyridine through acylamide to produce a novel chromophore (N-{4-[(2,2′:6′,2″-terpyridine)-4′-yl]benzyl}-9-hexyl-9H-carbazole-3-carboxamide, TBCC) for achieving programmable luminescence switches. Significantly different emission states, such as nonemissive, blue, green, yellow, red, and white, were achieved in situ by controlling sol–gel transformation with sonication/heat and the reversible metal–ligand coordination between TBCC and various metal salts. Based on this feature, an interacting network for multistate switching among six distinct emissive states was successfully constructed. Potential applications of the communicating network have been demonstrated for reversible multicolor encoding and decoding. These findings can be useful in the studies of molecular switches, dynamic assemblies, and smart materials. Download figure Download PowerPoint Introduction Similar to living organisms, some smart materials are known to alter their chemical and physical properties under the influence of external environmental changes.1–5 In recent years, these smart materials have drawn significant interest due to their wide range of applications in sophisticated technologies and daily life.6–8 In particular, research on multicolor emitting chromophores is of fundamental importance,9–11 as they can serve as key precursors in achieving advanced functions of signal generation,12–15 information storage and processing,16–18 displays,19–22 optical imaging,23–25 and anticounterfeiting.26–31 Control of molecular switches has been demonstrated as an effective way to modulate the luminescence conversion processes of chromophores.32–35 Research on external stimuli-triggered luminescence switching has also been widely reported.36–38 Although initial success has been achieved in attaining multicolored luminescence, most of them only exhibit up to a maximum of four emission states.39–42 The inability to obtain full-color interconversion remains a major challenge. Besides, most of the studies were based on mixed fluorophore systems.39,40 Development of a single molecule possessing multicolor switching capability is imperative since it can efficiently address the color aging issues due to photostability differences in mixed fluorophores.43,44 Therefore, the acquisition of full-color luminescence conversion in a single molecule is highly desirable because of its great potential in developing smart and light-emitting materials. Recently, control of the multicolor states following constitutional dynamic chemistry has been developed.45,46 For example, molecular networks have been created toward controllable multistate fluorescence colors by regulating the intermolecular dynamic covalent reactions among the various fluorophores.47–50 Also, the dynamic metal–ligand coordination is effective in modulating the multiple color states due to the reversible interaction between various metal salts and chromophores.51–54 In this study, we have designed and synthesized a carbazole-functionalized terpyridine-based chromophore (N-{4-[(2,2′:6′,2″-terpyridine)-4′-yl]benzyl}-9-hexyl-9H-carbazole-3-carboxamide, TBCC) to achieve multicolor emission states by using external stimuli. The TBCC shows significant enhancement in emission characteristics when it undergoes sol–gel transformation. Moreover, precise control of the dynamic metal–ligand coordination between different metal salts and TBCC ligand enables desirable multistate emission color switches in situ. Finally, the constructed communicating network with multistate emission color switching was used for dynamic multicolor encoding and decoding. Results and Discussion In our design, the core idea is to synthesize a small molecule gelator with a donor–acceptor structure containing a chelating motif whose optical properties can be markedly changed by employing a sol–gel transition. Such a gelator can be used in coordination with different zinc salts that alter the intramolecular charge-transfer state, thereby modifying the emission wavelengths. Moreover, characteristic luminescence can be generated after coordination between gelator and europium ion, which can further expand the emission color-tuning range. A combination of the stimuli-responsive supramolecular gel and the metal–ligand coordination-induced emission color switching is crucial in covering a wide emission spectral range. Importantly, the dynamic nature of sol–gel transformation and metal–ligand coordination enables the control of multicolor states and the creation of a communicating network. To test our hypothesis, we designed and synthesized a novel chromophore TBCC by incorporating a carbazole group into terpyridine through acylamide as depicted in Figure 1a. The carbazole group acted as an electron donor, and the terpyridine served as both an electron acceptor unit and chelating motif.55,56 The intermolecular π–π interactions and hydrogen bond of the acylamide unit, along with the long alkyl chain promoted molecular assemblies to form organogel. The detailed procedure for the synthesis of TBCC is provided in the Supporting Information Scheme S1. The synthesized tridendate ligand was characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), and 1H and 13C NMR spectroscopy Supporting Information Figures S10–S12. Figure 1 | (a) Chemical structure of TBCC and the functions of different groups. (b) Schematic description of the self-assembled TBCC to form one-dimensional fibers with fibrous networks. Download figure Download PowerPoint The gelation ability of TBCC was studied using the inverted vial method with different solvent mixtures ( Supporting Information Table S1). Results showed that TBCC can gelate in mixtures of N,N-dimethylformamide/ethanol (v∶v, 2∶9), N,N-dimethylformamide/H2O (v∶v, 1∶3), and dichloromethane/hexane (v∶v, 1∶3). The gelation process of TBCC is rapid in these mixtures with sonication, in which the minimum gelation concentration is about 50 mg mL−1. The formation of the supramolecular gel was most likely due to the intermolecular interactions between π–π stacking and hydrogen bonds as depicted in Figure 1b. Fourier transform infrared (FTIR) spectroscopy of the dried xerogel of TBCC showed an intense band at 3290 cm−1, which pointed out that strong hydrogen-bond interactions existed in the gel phase as depicted in Figure 2a. Scanning electron microscopy (SEM) imaging of the TBCC organogel showed a typically long fiber structure around 50 nm in width, as shown in Figure 2b. Due to the intense luminescence feature of the TBCC organogel, a confocal laser scanning microscope (CLSM) was employed to gain further insights into the nanostructure of the gel state. The CLSM image also confirmed the constructed one-dimensional (1D) fiber network, which is crucial for the generation of supramolecular gel (Figure 2c). The gel state was observed to be immediately transformed into to the solution state as depicted in Figure 3a when heated at 70 °C for 30 s, which shows that control of the sol–gel state is simple and fast. Figure 2 | (a) FTIR spectroscopy of the dried xerogel of TBCC and its corresponding metal complexes. (b) SEM and (c) CLSM images of the TBCC organogel. Download figure Download PowerPoint Furthermore, the gelation ability of TBCC with different metal salts has been investigated. It was revealed that the gelation ability is preserved up to 0.8 equiv addition of metal salts of ZnCl2, Zn(ClO4)2, or EuCl3 into TBCC solution. In addition, the sol–gel states can be readily regulated by ultrasound and heat. However, TBCC does not fully gelate above 0.8 equiv of metal salts and form a partial gel even after sonication, as shown in Supporting Information Figure S1. Analysis of the CLSM image of the partial gel (TBCC with 1 equiv ZnCl2), as depicted in Supporting Information Figure S2, reveals that fibrous networks cannot be efficiently constructed in the presence of excess metal ions, which explains why TBCC does not completely gelate. In short, incorporation of an appropriate amount of ZnCl2, Zn(ClO4)2, or EuCl3 into TBCC provides adequate opportunity to produce a switchable multicolor system. Figure 3 | (a) Schematic preparation of organogels with different emission colors under UV light. (b) Comparation of emission intensities of various organogels between solution and gel states. (c) PL spectra of TBCC (439 nm, quantum yield [QY] = 12.1%, τ = 14.2 ns), TBCC + ZnCl2 (491 nm, QY = 15.5%, τ = 311.5 ns), TBCC + Zn(ClO4)2 (532 nm, QY = 8.8%, τ = 34.3 ns), TBCC + EuCl3 (612 nm, QY = 0.3%, τ = 216.6 μs) in the gel state. (d) Photographs and (e) PL spectra of organogels in the presence of different amounts of Zn(ClO4)2 under UV irradiation. Download figure Download PowerPoint The photoluminescence (PL) properties of TBCC both in solution and gel states were studied. In a mixture of dichloromethane/hexane, TBCC manifested a very weak emission peak at 439 nm due to the photoinduced electron transfer (PeT) process from the amine unit to the terpyridine group. By contrast, the emission intensity was substantially enhanced 21.5 times after the formation of a supramolecular gel, as shown in Figure 3b. This is due to the intense hydrogen-bond interactions of –N–H···O=C in the gel state that interrupted the PeT process. Therefore, ON/OFF switchable emission can be readily achieved by controlling the reversible sol–gel transformation with sonication and heat. Furthermore, the PL properties of the supramolecular gel of TBCC with different metal salts of ZnCl2, Zn(ClO4)2, or EuCl3 were investigated Supporting Information Figures S3 and S4. The intramolecular charge transfer was increased by the addition of 0.5 equiv ZnCl2 as the electron-withdrawing ability of the terpyridine moiety within TBCC was enhanced.57 As a consequence, a remarkable redshift occurs from 439 to 491 nm, which indicates the change in the emission color from blue to green, as shown in Figures 3a and 3c. Coordination of Zn(ClO4)2 with TBCC results in a strong yellow fluorescence in the gel state due to the occurrence of a large bathochromic shift from 439 to 532 nm. In our previous report, we demonstrated that the change in the counterion with electronegativity is an efficient way to vary the intramolecular charge-transfer degree of the zinc complex.58 We know that the net charge quantity of the Zn2+ on the complex decreases with increasing counterion electronegativity. For TBCC–ZnCl2 complex, the zinc center may have less net charge because of the strong electronegativity of Cl−. Conversely, when weakly electronegative ClO4− was used as a counterion, the net charge on the Zn2+ was increased. Thus, the electron-withdrawing ability of the terpyridine unit would be consequently enhanced. Therefore, when the counterion was varied from Cl− to ClO4−, the lowest unoccupied molecular orbital (LUMO) levels were stabilized. Thus, the difference in emission wavelengths is because of the stabilization of the LUMO level induced by the decreasing electronegativity of counterions. Considering that blue and yellow are complementary emission colors, white light emission is anticipated to be achieved by the addition of an appropriate amount of Zn(ClO4)2. As shown in Figures 3d and 3e, blue, white, and yellow emissions were observed with an increase in Zn(ClO4)2 from 0.1 to 0.23, respectively Supporting Information Figure S8. Specifically, distinct white light emission with Commission Internationale de l′Eclairage (CIE) coordinates (0.29, 0.33) close to those corresponding to pure white light was obtained at 0.14 equiv Zn(ClO4)2. Similarly, red light emission was achieved by adding 0.5 equiv EuCl3 into TBCC. A strong red light-emitting supramolecular gel was produced by sonication of TBCC/EuCl3 mixture due to activation of the characteristic metal-center luminescence of europium ion at 612 nm by TBCC ligand. The CIE diagram comprising all distinct emission colors covering the entire visible spectral range is shown in Figure 4c. In addition, the reversibility of various organogels between their sol and gel states has been studied. As shown in Supporting Information Figure S5, the results showed that after 10 cycles of transformation between two states, the emission intensities were barely changed, indicating excellent reversibility. All emission colors can be reproduced in the dried xerogel, as shown in Supporting Information Figures S6 and S7, which predicts its promising potential applicability in a wide variety of areas. Figure 4 | (a) Schematic description of in situ control of emission colors through dynamic metal–ligand coordination. (b). The interconversion among six states (nonemissive, blue, green, yellow, red, and white) and associated photographs under UV irradiation. (c) CIE-1931 chromaticity diagram for various emission spectra. (d) The demonstration of reversible multicolor encoding and decoding. Download figure Download PowerPoint As shown in Figure 4a, multistate signal communication was further achieved by employing TBCC due to its sol–gel phase transformation and dynamic metal–ligand coordination-induced luminescence-switching characteristics. The interconversion between different emission color states is illustrated in Figure 4b and Supporting Information Figure S9. The blue color (state 2) was generated from luminescence off state 1 (solution state) by ultrasonication for 30 s, which could easily be reversed back to state 1 by heating. With the addition of 0.5 equiv ZnCl2 to state 1, the emission color was switched to green (state 3) through sonication. The transition from state 3 to state 1 is the key step in achieving other emission states. Tetrabutylammonium fluoride (TBAF) was used to dissociate the metal–ligand coordination between Zn2+ and TBCC to recover state 1, since fluoride ion has been demonstrated to show strong binding affinity with the Zn2+.59,60 Subsequently, state 5 (white emission) and state 6 (red emission) can readily be obtained by following the previous procedure. Consequently, a switchable multicolor network covering the entire visible emission range can be accomplished through the delicate manipulation of the sol–gel transformation and the dynamic metal–ligand coordination. It should be noted that all emission color switches in the network were accomplished in situ, suggesting excellent switchability and recyclability. The aforementioned results impelled us to create a dynamic platform for multicolor information encoding and decoding. Thus, the TBCC dichloromethane/hexane mixture was used to record invisible information in vials. After sonication for a few seconds, three Arabic numbers “123” with strong blue fluorescence appeared (Figure 4d), which could then disappear when heated at 70 °C for 30 s. The number “123” in yellow, green, and red appeared after sonication of TBCC with 0.5 equiv Zn(ClO4)2, ZnCl2, and EuCl3, respectively. A similar switching process between different emission states can be accomplished by using ultrasound, heat, TBAF, and different metal salts. This result also increased the complexity and enriched the information showing great potential in multilevel data encryption and logic gates. Conclusion A compound consisting of carbazole and terpyridine group was designed to achieve OFF/ON emission switch through the regulation of its sol–gel transformation by ultrasound and heat. Furthermore, by combining the dynamic metal coordination-induced emission color variations of TBCC, a communicating network consisting of six distinct emission states was constructed in situ. Eventually, tunable multicolor displays were successfully achieved. To the best of our knowledge, this is the first demonstration of obtaining six distinguishable emission states in a single chromophore. Overall, this facile and powerful strategy for luminescence color modulation is promising for a wide range of photonic applications, such as multicolor display, information encryption and decryption, logic gates, and so forth. Supporting Information Supporting Information is available. Conflict of Interest The authors declare no conflict of interest. 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Google Scholar Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 3Issue 9Page: 2437-2444Supporting Information Copyright & Permissions© 2020 Chinese Chemical SocietyKeywordsorganogelmolecular switchesmulticolor luminescencestimuli-responsive materialsmetal–ligand coordinationAcknowledgmentsNational Funds for Distinguished Young of China (no. 61825503) and National Natural Science Foundation of China (nos. 62075101, 21701087 and 61775101). Downloaded 1,222 times PDF downloadLoading ...