Chain-stiffening enhanced ultralong organic phosphorescence in high glass transition temperature polymers

Abstract

Polymer-based phosphorescent materials with excellent processability and thermal stability are essential for organic optoelectronic applications. However, developing high-performance polymer-based room-temperature phosphorescence materials remains a significant challenge due to extensive macromolecular chain mobility, which leads to exciton dissipation and phosphorescence quenching of chromophores. Herein, we present a straightforward strategy to stiffen the polymer chains to restrain chain mobility for achieving ultralong organic phosphorescent emission. As a result, these polymeric phosphorescent materials have a high glass transition temperature (T_g) of 165 °C and exhibit an ultralong-lived RTP emission lifetime of 3.89 seconds. The universality of the design principle was further verified by doping various chromophores into the rigid polymer matrix. Given the ultralong phosphorescence lifetimes of the materials, we demonstrated their potential application in information encryption. These findings provide a strategic guideline for designing ultralong-lived room temperature phosphorescent polymeric materials.

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Long Gu

Dr Long Gu received his PhD in 2018 from Nanjing Tech University and subsequently carried out postdoctoral research at Nanyang Technological University, Singapore, from 2018 to 2020. In 2021, he joined the Institute of Flexible Electronics at Northwestern Polytechnical University as a professor. His research centers on the design, synthesis, and functional investigation of organic optoelectronic materials, including room-temperature phosphorescent materials, functional supramolecular polymers, and organic scintillators. He explores their advanced applications in data encryption, imaging, detection, and chemical and biological sensing.

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Introduction

Organic room-temperature phosphorescent (RTP) materials have garnered significant attention in recent decades, driven by their broad potential applications in fields such as organic light-emitting diodes, bio-imaging, radiation detection, anti-counterfeiting, and more.^1–5 Nevertheless, achieving RTP in purely organic materials remains a great challenge owing to the intrinsic weak spin–orbit coupling (SOC) and substantial non-radiative decay of triplet excitons of the organic chromophores at room temperature.^6–9 To address these challenges, various construction strategies aimed at enhancing intersystem crossing (ISC) and suppressing non-radiative transitions have been extensively explored, including crystal engineering, polymer engineering, host–guest doping, and metal–organic frameworks (MOFs).^10–18 Among them, polymer-based RTP materials have garnered particular interest due to their lightweight nature, superior processability, transparency, and thermal stability.^19–22 Currently, most polymer-based RTP materials are produced by covalently attaching aromatic chromophores to polymer chains or by physically doping chromophores into a polymer matrix.²³ Based on these strategies, a diverse array of polymer-based RTP materials has been successfully developed by employing different polymer matrices, including polylactic acid (PLA), poly(methyl methacrylate) (PMMA), poly(vinyl alcohol) (PVA), and polyacrylonitrile (PAN).^24–29

Despite significant progress in suppressing non-radiative decay pathways of polymeric RTP materials, the predominant strategy remains focused on restricting the motion of organic phosphors by fabricating covalent bonds or non-covalent interactions between the polymeric matrices and organic chromophores.^30–34 Nevertheless, another critical factor that is often overlooked in the development of high-performance polymer-based RTP materials is the intrinsic flexibility and deformability of polymer chains, which can lead to significant non-radiative decay and triplet exciton dissipation.^35,36 Generally, improving the glass transition temperature (T_g) has been widely proven to be an effective strategy for restricting the motion of flexible polymer chains.^37–40 To the best of our knowledge, however, there are hardly any strategies that have been proposed to construct high T_g RTP materials by stiffening the polymer chain.

Herein, we synthesized a type of polymer-based RTP material with high T_g by introducing strongly rigid and polar side chain groups (Fig. 1). The selected rigid methoxy-containing benzonitrile, incorporated into the methacrylate skeleton, can significantly enhance chain rigidity and improve interactions between the guest molecules and the polymer chains. This creates a rigid microenvironment that reduces non-radiative transitions of triplet excitons caused by the molecular motions of chromophores.^41–43 As a result, these RTP polymers exhibited a high T_g of 165 °C and an ultralong phosphorescence emission lifetime of 3.89 seconds. Furthermore, the DSC experiment and theoretical simulation revealed that the high T_g of these polymers as hosts of chromophores can efficiently suppress the non-radiative pathways of chromophores to achieve ultralong RTP.

Fig. 1 A schematic illustration of RTP materials made from high glass transition temperature polymers. Here, T_g denotes the glass transition temperature.

Results and discussion

We first synthesized three copolymers by radical copolymerization, namely poly(4-hydroxybenzonitrile)methacrylate (PBM), poly(vanillinitrile)methacrylate (PVM), and poly(butyronitrile)methacrylate (PSM), respectively (Fig. S1, ESI†). The chemical structures were characterized by nuclear magnetic resonance (NMR) spectroscopy, high resolution (HR) mass spectrum and High-performance liquid chromatography spectrum (Fig. S2–S21, ESI†). The molecular weights of PBM, PVM, and PSM polymers were determined by gel permeation chromatography (GPC) (Fig. S15 and Table S1, ESI†). Additionally, the photoluminescence (PL) and phosphorescence (Phos) spectra, along with their corresponding excitation spectra, revealed relatively weak emission characteristics for these polymer matrices (Fig. S22–S24, ESI†). Subsequently, we selected the guest chromophore of 7H-dibenzo[c,g]carbazole (DBCz) as our research model, doping it into PBM, PVM, and PSM films to obtain polymer-based RTP materials, respectively (Fig. 2a). As anticipated, after switching off the ultraviolet (UV) lamp, DBCz@PBM, DBCz@PVM and DBCz@PSM films exhibited the yellow afterglow lasting about 5, 7, and 3 seconds, respectively (Fig. 2b). To investigate this ultralong organic phosphorescence phenomenon, we performed the photoluminescence (PL) and phosphorescence (Phos.) spectra of these polymer films at room temperature. As shown in Fig. 2c and Fig. S25–S27 (ESI†), the steady-state spectra of DBCz@PBM, DBCz@PVM, and DBCz@PSM showed a blue emission band at around 395 nm, while delay spectra revealed major yellow–green emission in the range of 450–600 nm. Additionally, the emission decay profiles of the three polymer films at the maximum peak of 395 nm exhibited lifetimes of 4.07 ns, 4.59 ns, and 2.97 ns, corresponding to classic fluorescence emission (Fig. S28, ESI†). Meanwhile, the phosphorescence emission peaks of DBCz@PBM, DBCz@PVM, and DBCz@PSM at around 520 nm displayed lifetimes of 1037.1 ms, 1222.8 ms, and 610.5 ms, respectively, which were ascribed to the phosphorescence feature (Fig. 2d and Table 1). Notably, compared to DBCz@PSM, the RTP lifetimes from DBCz@PBM to DBCz@PVM showed a dramatic enhancement upon introducing methoxy groups. This result might be attributed to the larger side-chain volume in PVM, which can effectively restrict the motion of polymer chains to generate ultralong phosphorescence emission. Meanwhile, DBCz@PSM exhibited a shorter lifetime despite having larger side chains. This unexpected decrease might arise from the excessive steric bulk, allowing oxygen diffusion into the polymer matrix and subsequently quenching the triplet-state of chromophores. In addition, oxygen sensitivity experiments validated this hypothesis. Compared to the DBCz@PBM and DBCz@PVM, the phosphorescence emission intensity of DBCz@PSM displayed a significant decrease when the samples were exposed to an oxygen atmosphere for 10 minutes at room temperature (Fig. S29, ESI†). Moreover, the gradual increase of phosphorescence intensity and lifetime from DBCz@PBM to DBCz@PVM and to DBCz@PSM under vacuum conditions further confirmed the exceptional oxygen sensitivity of PSM (Fig. S30 and S31, ESI†). These results demonstrated that tuning the side-chain size is an effective strategy for enhancing both stability and ultralong organic phosphorescence, especially in vacuum conditions.

Fig. 2 (a) Chemical structures of the guest and polymer hosts. (b) Photographs of DBCz@PBM, DBCz@PVM and DBCz@PSM films taken under a 365 nm lamp on and off. (c) Photoluminescence (PL) and phosphorescence (Phos.) spectra of DBCz@PVM films excited by 290 and 340 nm under ambient conditions, respectively. (d) Lifetime decay curves of DBCz@PBM, DBCz@PVM and DBCz@PSM films of emission band at 520 nm, respectively. (e) Phosphorescence (Phos.) spectra of DBCz@PVM films at various doping concentrations.

Table 1 Summary of the photophysical data of the polymer-based UOP materials

Sample	Fluo.			Phos.
	λ em (nm)	τ (ns)	Φ Fluo. (%)	λ em (nm)	τ Phos (nm)	Φ phos. (%)
DBCz@PBM	395	4.1	17.0	520	1037	1.1
DBCz@PVM	395	4.6	18.8	520	1223	1.11
DBCz@PSM	395	3.0	9.8	520	611	0.84

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In a subsequent set of experiments, we systematically investigated the effect of the content of the guest emitter of DBCz on the room temperature phosphorescence properties of the polymer films. Given the longest RTP lifetime observed in the DBCz@PVM film, we selected it as the model polymer host for further investigation. As shown in Fig. 2e and Fig. S32 (ESI†), the phosphorescence intensity of the DBCz@PVM film progressively increased as the weight feed ratio was raised from 0.01 to 0.1 under UV light excitation. However, further increasing the feed ratio from 0.1 to 0.7 resulted in a gradual decline in phosphorescence intensity. Meanwhile, the similar trend was observed in phosphorescence efficiency (Table S2, ESI†). Moreover, the phosphorescence lifetime of the DBCz@PVM film exhibited a similar decreasing trend. When the weight feed ratio was 0.3, the polymer showed the longest lifetime of 1275.4 ms (Fig. S33 and S34, Tables S3 and S4, ESI†). The declining trend in both phosphorescence intensity and lifetime at high weight feed ratios might be attributed to aggregation-caused quenching of triplet excitons, which resulted from the presence of excessive chromophores in the PVM polymer film. Similar phenomena were also observed in the DBCz@PBM and DBCz@PSM, which had the highest phosphorescence intensity at a weight feed ratio of 0.1 (Fig. S35–S42, and Tables S5–S10, ESI†). From these findings, the optimal doping concentration of 0.1 wt% for the emitter was selected for subsequent investigations.

To further elucidate the ultralong room temperature phosphorescence mechanism of these polymeric materials, the control experiments of DBCz molecules in both dilute solution and polymer matrix were conducted. As shown in Fig. 3a and Fig. S43 (ESI†), the phosphorescence bands of DBCz@PVM at 520 nm, 570 nm and 605 nm at room temperature were consistent their corresponding isolated molecule phosphorescence emission bands in the dilute m-THF solution (1 × 10⁻⁵ M) at 77 K. Simultaneously, time-dependent density functional theory (TDDFT) calculations on DBCz molecule revealed that the lowest singlet (S₁) and triplet state (T₁) of isolated DBCz in the gas phase were located at 365 and 574 nm, closely matching the experimental peaks at 395 nm and 570 nm (Fig. 3b). These experimental and theoretical results indicated that the ultralong phosphorescent emission of the polymer originated from the DBCz chromophore, rather than the polymer matrix. The polymer matrix was employed to restrain the motions of chains and chromophores, thereby suppressing the non-radiative transition of triplet excitons. Furthermore, the phosphorescence spectra of the DBCz@PVM film at room temperature resembled the results in the solution at 77 K, indicating that the polymer matrix mimics cryogenic rigidity at ambient conditions to stabilize triplet states for ultralong RTP emission.

Fig. 3 (a) Normalized steady-state photoluminescence (black lines) and phosphorescence spectra (blue lines) of DBCz in PVM film under ambient conditions (top) and in dilute m-THF solution (1 × 10⁻⁵ M) at 77 K (bottom). (b) Natural transition orbitals (NTO), energy diagram and spin-orbital coupling (ξ) of DBCz. (c) Glass transition temperature (T_g) of PBM, PVM, and PBM. (d) Electrostatic potential (ESP) of BM, VM, and SM monomers. (e) Plausible mechanism for ultralong room-temperature phosphorescence in high glass transition temperature PVM films.

To gain a deeper insight into the influence of polymer matrices on the RTP performance, we conducted differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) measurements to assess the thermal properties of the polymers. As shown in Fig. 3c, Fig. S44 and S45 (ESI†), by increasing the number of methoxy groups on the aromatic polymeric side-chains, the polymers presented a gradual increase in T_g, rising from 105 °C for PBM to 130 °C for PVM, and reaching 165 °C for PSM. This significant increase could be attributed to the strong dipolar interactions between polymeric chains and bulkier steric hindrance of the polymeric side-chains. This led to reduced segmental mobility, thereby elevating the T_g. To validate this, electrostatic potential and dipole moment analyses of monomers were performed, respectively. As shown in Fig. 3d, the electron density surfaces around the cyano group exhibited a negative electrostatic potential, whereas those around the methoxy group showed a positive potential. Moreover, the uneven distribution of electrostatic potential (ESP) became more pronounced as the number of methoxy groups increased from BM to VM to SM. Additionally, the dipole moment values of BM, VM, and SM were calculated and found to increase from 4.26 D, 5.72 D, to 5.91 D with the increasing number of methoxy groups. Considering all these results, we concluded that this enhancement in polarity and dipole moment can improve the intermolecular dipole–dipole interactions and strengthen polymer interchain interactions, thereby suppressing the movement of polymeric chains. Simultaneously, introducing additional methoxy groups in rigid planar benzonitrile could restrain the rotation of side-chains for improving the rigidity of the polymers. These factors collectively contributed to the chain-stiffening of the polymers, increasing the glass transition temperature (T_g) and reducing the segmental mobility of the polymer chains. As a result, the nonradiative transitions of triplet excitons in chromophores were effectively suppressed, thereby enabling the generation of ultralong phosphorescence emission.

Taken together, we proposed a plausible mechanism for the ultralong phosphorescence emission in high glass transition temperature polymer-based materials at room temperature. As shown in Fig. 3e, upon UV irradiation, the chromophores could generate the triplet excitons by the efficient intersystem crossing from their singlet excited states. Meanwhile, the strong polymer interchain interactions and the bulkier steric hindrance created a rigid high-T_g polymer matrix that constructed a constrained microenvironment, suppressing vibrational relaxation and reducing collisional quenching pathways of triplet excitons. Therefore, the triplet state excitons could be stabilized, thereby prolonging the emission lifetime of the triplet excitons. As a result, this series of high T_g polymer-based RTP materials exhibited exceptional ultralong-lived room-temperature phosphorescence emission, outperforming conventional polymer RTP systems.

To further validate the generality of our strategy, two additional phosphorescent emitters, coronene (Cone) and 4′-(diphenylamino)-4-hydroxy-[1,1′-biphenyl]-3-carbonitrile (TPCN), were selected as guest molecules and dispersed into the PVM polymer matrix at a weight feed ratio of 0.1, named Cone@PVM and TPCN@PVM, respectively (Fig. S46 and S47, ESI†). As expected, both Cone@PVM and TPCN@PVM films exhibited strong yellow afterglow emission after ceasing UV illumination. As shown in Fig. 4a and b, and Fig. S48 and S49 (ESI†), the maximum emission peaks of Cone@PVM and TPCN@PVM were located at 394 nm and 424 nm in steady-state PL spectra, while their phosphorescence spectra showed a structured emission band between 500 and 650 nm. The similar phosphorescence emission peaks were also observed in the dilute solution of Cone and TPCN at 77 K (Fig. S50–S52, ESI†). Based on these experiments, we concluded that the high T_g PVM matrix, with its rigid polymer chain architecture, established a densely confined microenvironment that effectively stabilized and protected the embedded Cone and TPCN chromophores. In addition, it was worth noting that the emission lifetimes of Cone@PVM at 570 nm and TPCN@PVM at 548 nm were 3.89 s and 383.7 ms under ambient conditions, respectively (Fig. 4c, Fig. S53 and Table S11, ESI†). Furthermore, Cone@PVM and TPCN@PVM all exhibited increased phosphorescent lifetimes up to 4.24 s and 465.7 ms under vacuum conditions (Fig. S54–S56, ESI†). To the best of our knowledge, it is rarely reported ultralong phosphorescence over 3 s in polymer-based materials under ambient conditions (Table S12, ESI†).^44–48 These experiments further demonstrated that limiting the mobility of macromolecular chains in high-T_g RTP polymers was an effective strategy for developing ultralong-lived polymer-based RTP materials.

Fig. 4 (a) Normalized steady-state photoluminescence (black line) and phosphorescence spectra (green line) of Cone@PVM film under ambient conditions. (b) Photographs of Cone@PVM films taken under a 365 nm lamp on and off. (c) Lifetime decay curve of Cone@PVM films at 570 nm. (d) Experimental setup for the anti-counterfeiting display device. (e) Demonstration of Morse Code anti-counterfeiting using the DBCz@PVM.

Applications

Given the different ultralong afterglow emission lifetimes based on the PVM polymer matrix, the potential applications in afterglow display and information encryption were demonstrated. Initially, we fabricated the digit “8” as anti-counterfeiting patterns using DBCz@PBM, DBCz@PVM, and DBCz@PSM film. As shown in Fig. 4d, these films exhibited intense blue fluorescence under 365 nm UV irradiation. Nevertheless, after removing the excitation source, the digit “8” with the ultralong yellow afterglow can be observed with the naked eye. Notably, approximately 1 s after ceasing UV irradiation, the luminescent pattern transformed into the digit “3” due to the rapid decay of phosphorescence emission of DBCz@PBM and DBCz@PSM. This time-resolved luminescent display provided a promising approach for next-generation dynamic information encoding and anti-counterfeiting applications. In addition, this ultralong afterglow material was integrated with Morse code to enable more advanced information encryption and display. As demonstrated in Fig. 4e, the encrypted information “NPU” was clearly distinguishable in the DBCz@PVM film before and after UV exposure, highlighting its potential for secure optical data storage and authentication.

Conclusion

In summary, we developed an effective strategy to enhance the room-temperature phosphorescence performance of polymer-based RTP materials by restricting the motion of polymer chains through increasing the glass transition temperature. The polymer chain stiffening was achieved by introducing rigid and polar side groups, resulting in a polymer with a relatively high T_g of 165 °C. By embedding chromophores into these polymer matrices, we successfully prepared a series of ultralong-lived organic phosphorescent materials with the longest lifetime of 3.9 seconds. These high T_g polymer matrices can suppress the non-radiative transitions of guest chromophores, facilitating exciton stabilization and improving the phosphorescence lifetime of the embedded chromophores. This study offers valuable insights for designing and synthesizing novel, high-performance polymer-based organic phosphorescent materials.

Author contributions

L. Gu and Y. Gao conceived the projects. Y. Wu, H. Chen and M. Dong conducted the experiments. Y. Wu, M. Dong, and Z. Long measured the spectra. Y. Wu, M. Dong, J. Shan, Z. Long, H. Chen, Y. Gao, and L. Gu analyzed the data, wrote, and revised the manuscript. All authors discussed the results.

Data availability

All data supporting the findings of this study are available within the article and its ESI.†

Conflicts of interest

There are no conflicts to declare.

Acknowledgements

This research is supported by the National Natural Science Foundation of China (22475172 and 52203242), and the Zhejiang Provincial Natural Science Foundation of China under Grant No. LQ23B020004, and the Fundamental Research Funds for the Central Universities.

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Footnotes

† Electronic supplementary information (ESI) available: Synthesis and additional NMR characterization; DFT calculation; TGA and DSC curves; additional optical properties. See DOI: https://doi.org/10.1039/d5tc01657f

‡ H. Chen and M. Dong contributed equally to this work.

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