Di
Zhao
,
Xianglong
Li
,
Qianrui
Li
,
Chunmei
Yue
,
Yige
Wang
* and
Huanrong
Li
*
School of Chemical Engineering and Technology, Hebei University of Technology, GuangRong Dao 8, Hongqiao District, Tianjin 300130, P. R. China. E-mail: lihuanrong@hebut.edu.cn
First published on 19th July 2024
Photo-responsive luminescent materials capable of responding to light stimuli are crucial in the realm of sophisticated encryption, anti-counterfeiting, and optical data storage. Yet, the development of such materials that also feature self-healing capabilities, swift reaction times, light weight, fatigue resistance, dynamic display abilities, and enhanced security measures is exceedingly rare and presents considerable challenges. Herein, a novel family of self-healing and photo-stimuli-responsive photoluminescent polymers are reported, which is achieved by interlinking terpyridine- and spiropyran-functionalized polymers through N–Ln coordination bonds and hydrogen bonding among the polymer chains. The resulting polymers exhibit good processability, superior tensile strength, fast self-healing ability, and photo-stimuli-responsive performance. The photo-stimuli-responsive properties include unique color shifts (colorless and purple) and light-controlled time-dependent fluorescence modulation (green-, red-, and yellow-emission), which stem from fine-tuning the isomerization of spiropyran and leveraging the fluorescence resonance energy transfer (FRET) from Ln–Tpy donors to spiropyran acceptors, respectively. Besides, these polymers have been successfully applied in dynamic multi-level information encryption applications. We are convinced that these smart materials, crafted through our innovative approach, hold vast potential for applications in information storage, cutting-edge anti-counterfeiting encryption, UV-sensing, and light-writing technologies, marking a novel strategy in the design of photosensitive luminescent smart materials.
However, the fluorochromic and chromogenic properties in most lanthanide-based studies are mainly obtained via the alternating use of different chemical substances (such as ions, acid/alkali, or water) due to the chemical responsiveness feature of these materials.7,8 These systems are prone to suffer from the residue/accumulation of chemicals, which would largely reduce the cyclability, durability, reliability, and sensitivity. Light radiation is a green stimulus due to its non-invasiveness and nondestructive nature, submicron- or micron-sized focusing area, controllable energy, time and wavelength, remote control, and precisely controlled direction.9 Currently, many elegant photoswitching materials have been reported, in which the implementation of photoswitching ability relies on certain special molecules with chemical structure conversion capacities triggered by light, such as diarylethene (DAE),10 spiropyran (SP),11,12 azobenzene (AZO),13 phosphomolybdic acid hydrate (PMA),14etc. Among them, spiropyran (SP) has been widely exploited and used in multiple-level encryption fields because it can transform from a non-luminescent closed-ring structure to a luminescent open-ring merocyanine (MC) isomer on UV light treatment and can restore its initial state on visible-light treatment.15,16 For example, Tang and his colleagues reported a photosensitive material based on naphthalene and spiropyran, which can be applied to a three-level information encryption platform by artificial design.17 Cui's team reported a visible-light-driven photosensitive fluorescent material based on functionalized spiropyran and applied it to the field of dual-level information anti-counterfeiting encryption.18 Introducing spiropyran units into the lanthanide-based photoluminescent materials will inevitably combine the advantages of both into one system.
Within a diverse array of sophisticated lanthanide-based materials, including metal–organic frameworks (MOFs),19 hydrogen-bonded organic frameworks (HOFs),20,21 conventional solid powders,22 and hydrogels,23 polymer matrices stand out for their ease of processing, robust mechanical characteristics, and versatile functionalities.24 Despite these advantages, conventional polymers tend to suffer from damage and breakage due to use, highlighting the essential need to enhance these materials with self-healing properties for sustained durability and performance.25 Fortunately, the Ln–ligand coordination bonds and hydrogen bonds within the polymer chains provide the possibility to endow the lanthanide-based polymer with self-healing ability owing to their dynamic nature, which can autonomously repair physical damage, restore the original functions, extend service life, and reduce waste and maintenance costs.26–28 We envision that this multifunctional intelligent material, which combines color changes (absorption), fluorescence variations (emission), processing performance, mechanical properties, and self-healing properties, will inevitably generate new possibilities. However, no such studies have been reported yet, to the best of our knowledge.
In this work, we develop a family of advanced, multifunctional intelligent polymers, combining exceptional mechanical properties, swift light-responsiveness, efficient processability, recyclability, and fast self-healing behavior, by intertwining terpyridine (Tpy)- and spiropyran (SP)-modified polyurethane chains through Tpy–Ln coordination and hydrogen bonds within the polymer framework. Spiropyran stands out as a key photosensitive element in light-activated systems, capable of switching between its closed-ring (SP) and open-ring merocyanine (MC) forms upon exposure to alternating UV and visible light, making it an integral photosensitive component of the polymer structure. The lanthanide complexes retain the exceptional luminescence qualities of the respective Ln3+ ions while also ensuring spectral overlap with the MC-state of spiropyran to modulate the photoluminescence of the polymers by using photo-stimuli. Leveraging the synergistic properties of Tpy–Ln and spiropyran, the well-known Förster resonance energy transfer (FRET) process from the Tpy–Ln donor to the spiropyran acceptor was induced by UV irradiation, and swift fluorescence color modulation (including green to red, yellow to red and green to yellow) along with distinct color transformation (colorless to purple) ability was achieved. The color and luminescence properties of the resultant deep purple polymer could be restored upon visible light irradiation. In addition to comprehensively exploring the superior performance of our polymers, these polymers have been successfully employed in dynamic and controllable applications of multi-level information encryption. We are confident that these advanced, multifunctional intelligent polymers will inevitably pave the way in the fields of sophisticated information encryption and multi-level anti-counterfeiting technologies.29–31
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Fig. 1 (a) Chemical structure conversion illustration of spiropyran from a closed-ring structure (SP) to an open-ring merocyanine (MC) isomer. (b) A simple schematic diagram of the chemical structure of samples P2 and P3 (for P2, Ln = Tb3+; for P3, Ln = Eu3+; please refer to Fig. S1† for the specific chemical structure). (c) Transmission spectra of photosensitive behavior of the representative sample P2. (d) Processing ability and photo-controlled luminescence modulation capability of the representative sample P2. |
After treating photosensitive polymer P2 with 365 nm ultraviolet or visible light, there was no significant change in its mechanical properties (Fig. 2c). This observation indicates that the luminescence switching process does not affect the mechanical behavior of the metal–polymer, i.e., its open and closed isomerization does not affect the polymer network.37 The outstanding mechanical properties can also be proved via a load-bearing measurement and puncture resistance experiment. As shown in Fig. 2d, a 3 kg reaction kettle bucket could be lifted by a 92 mg P2 sample strip, whose weight is more than 32600 times that of the P2 strip. Then, we fixed the strain of a 0.2 mm thick photosensitive sample at 500%, and the sample was not punctured by a 0.7 mm sharp steel needle under manual sideway stretching (Fig. 2e). Also, the synthesized photosensitive polymers exhibit fast elastic restorability, indicating fatigue resistance and reliability of the materials during repeated deformation. As shown in Fig. S11,† after sideway stretching and release under a fixed deformation of 500%, the stretched P2 recovered instantly like a piece of rubber. Similar to typical elastomers reported previously,38,39 the prepared polymers also exhibit a certain degree of viscoelasticity, which can be demonstrated through cyclic tensile testing. As shown in Fig. S12,† significant hysteresis was obtained, during the continuous loading and unloading tensile tests, indicating the presence of energy dissipation (the specific values are summarized in Table S3†), which is ascribed to the dissociation/recombination of dynamic crosslinking bonds that cannot be fully restored to their original state at a single cyclic time scale.40,41
Next, the self-healing performance of the photosensitive polymers was studied. As shown in Fig. S13 and Video S1,† the fractured P2 sample can withstand a strain of 150% after self-healing for only 2 min. To further determine the self-healing ability, P2 samples were bisected and allowed to self-heal at room temperature (RT) for different times, and then stretched until failure again. The stress, stain and toughness of the samples were restored to 7.49 ± 0.53 MPa, 1144 ± 31% and 59.33 ± 0.30 MJ m−3, respectively, after self-healing at RT for 24 h, without any external stimulus (Fig. 2f and Table S4†). Moreover, the healing ability of P2 can be improved by heating. The stress, strain and toughness of P2 recover to 1842 ± 33, 14.92 ± 0.43 MPa and 140.25 ± 10.3 MJ m−3, respectively, after self-healing at 60 °C for 24 h (Fig. 2f and Table S4†). The self-healing properties of the prepared polymers originate from the dynamic nature of hydrogen bonds and Tpy–Tb coordination interactions, which can be demonstrated by alternate step strain rheological measurement.42 As shown in Fig. 2g, the elastomer can transfer from the solid state (G′ > G′′) at 0.1% shear strain to the liquid state (G′ < G′′) at 100% strain due to the breaking of the dynamic networks. After the strain recovers to 0.1%, the fractured dynamic bonds are reconstructed and the polymer network is restored to the solid state again (G′ > G′′) and the responses of our polymer can rapidly alternate between the above two states. The non-crystallized loose structure (Fig. S7†) and low Tg (−53 °C, see Fig. S5†) also provide a driving force for the diffusion and movement of polymer chains, thereby promoting the self-healing behavior of the material.43
As a comparison, our photosensitive material P1 has a higher self-healing efficiency than that of P2 at room temperature for a short self-healing time (0.5, and 3 h) (Fig. S14 and Tables S4, S5†). With the increase in self-healing time (12, and 24 h), the self-healing efficiency of P2 exceeds that of P1. In addition, the self-healing efficiency of P2 will also be higher than that of P1 after increasing the temperature (Tables S4 and S5†). We speculate that the above phenomenon is due to the absence of Tpy–Ln coordination bonds in P1, which leads to higher diffusion of polymer chains at room temperature and facilitates the self-healing of damaged materials. As the temperature increases, polymer chains undergo thermally induced movement and diffusion, and the dynamic properties of Tpy–Ln coordination bonds drive the self-healing performance of the polymer. Furthermore, the obtained photosensitive polymers can be dissolved in DCM solvents, and then be re-cast and dried to obtain recycled samples. The mechanical properties and photosensitivity of the recovered samples are maintained, indicating that our materials have good reusability and recycling ability (Fig. S15†).
After exposure to 365 nm UV light for 15 s, the spiropyran unit within the luminescent polymers switched from ring-closed SP to the ring-open merocyanine form (MC), and the material rapidly transformed into a deep purple color (see Video S2† and Fig. 1), which generates new absorption bands in the range of 445–650 nm. This 445–650 nm absorption range overlaps with the luminescence emission range of the Tpy–Tb components, and therefore efficient photoinduced FRET from Tb3+ to MC in the polymers arose (Fig. 3d). Therefore, the luminescence intensity of Tpy–Tb in the material was quenched by 90.13% with concomitant decreases in the 5D4 decay times from 0.62 to 0.36 ms (Fig. 3e). According to the previously reported method, the FRET efficiency in the polymer was calculated to be 42%.45,46 Meanwhile, due to the addition of red-emission (characteristic broadband centered at 625 nm) originating from MC, the luminescence changed from green to a clear yellow-emission under 302 nm UV light, and luminescence transformed from green-emission to bright-red-emission under 365 nm UV light (Fig. 4a). Moreover, the color and luminescence properties of the resultant deep purple polymer could be restored to the initial state upon visible light irradiation for only 15 s, arising from the regeneration of SP (Video S2†).
Notably, the reversible and prominent luminescence photosensitive behavior of P2 could be steadily switched by alternating UV and visible-light irradiation, and the minimum and maximum PL intensities at 545 nm do not present obvious decay (Fig. 4f). The cyclic characteristics can be reproduced at least ten times without fatigue, indicating that the obtained photosensitive polymer has excellent stability and fatigue resistance as a potential dynamic fluorescent material. As for P1 and P3, their PL spectra and CIE diagrams also correspond to their digital photos (Fig. 4a, g, h and S17†).
Usually, traditional luminescent encryption materials can be easily identified and have hidden dangers due to the characteristics of single-level encryption modes.47,48 Therefore, it is necessary to develop higher levels of protection for information storage and passing. We believe that the photosensitive materials prepared by us feature broad application prospects in the field of information anti-counterfeiting due to their ability to simultaneously change color (absorption) and show various time-dependent photosensitive fluorescent color changes (emission) in response to external light stimuli. As shown in Fig. 4c, a pattern anti-counterfeiting platform was constructed via P1, P2, P3, and P4 (for distribution of various samples, see Fig. S19†). The color change (for first-level encryption) (see Fig. 4c) and time-dependent photosensitive fluorescence under 365 nm UV light (for second-level encryption) can be realized (Fig. 4d), indicating their unique applicability in the field of anti-counterfeiting. Interestingly, different parts of the material can quickly self-heal and bear their own weight after coming into contact with the fracture surface of the cut material, even though there is only a very small contact area of the fracture surface due to the lightweight nature and fast room temperature self-healing ability of the obtained materials (Fig. 4c).
In addition, carefully crafted and well-designed multiple-level information encryption matrices can also be achieved, which calls for two consecutive actions to unveil the encrypted information. These two consecutive actions are (i) irradiating the information matrices at 365 nm for 15 s, and (ii) observing the information formed by the yellow lattice as real information. As shown in Fig. 4e, we set information “711” formed by the yellow lattice as correct information. Initially, there is no information available in the 5 × 11 transparent sample arrays under daylight (for first-level encryption), and information “811” and “1811” can be detected under 302 and 365 nm UV light, respectively (for second-level encryption). Subsequently, after exposure to 365 nm UV light for only 15 s, the information “1671” and “761” can be identified under daylight (for third-level encryption), information “711”, “1711” and “1811” can be detected at 302 nm, “1761”, and “1861” can be detected at 365 nm (for fourth-level encryption). So, a fourth-level information encryption platform was achieved. The sample information arrays can be restored to their original state and encrypted again by exposure to visible light for 15 s. Among the above-mentioned P1, P2 and P3 pixel samples, there is also a time-dependent photosensitive fluorescence behavior (please refer to Fig. 4d), which also plays a role in advanced anti-counterfeiting.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d4sc02733g |
This journal is © The Royal Society of Chemistry 2024 |