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. 2025 Nov 26;16:11120. doi: 10.1038/s41467-025-66035-w

Nonconventional near-infrared room-temperature phosphorescent materials based on spiropolymer alloy

Yue Ren 1,2,#, Yongfeng Zhang 2,#, Han Su 2, Yeyun Zhao 2, Wenya Yan 2, Wenbo Dai 2, Luojie Zhu 2, Tao Wang 2, Jianbing Shi 2, Junge Zhi 3, Bin Tong 2, Peng Sun 4,5,✉, Zhengxu Cai 2,5,✉, Yuping Dong 2
PMCID: PMC12705653  PMID: 41298422

Abstract

Near-infrared room-temperature phosphorescent (NIR-RTP) materials feature the advantages of large Stokes shift, long emission lifetime, and high penetration ability, and have been broadly applied in bio-medical imaging, fiber optic telecommunication, and night vision-readable display. Developing organic NIR-RTP materials heavily relies on the long-conjugated chemical structures. The large conjugation could result in aggregation caused quenching, complex synthesis, poor processability, and high biological toxicity. Herein, by solution blending poly(iminofuran-spiro-pyrrolone) (PISP) with polystyrene (PS), we construct a nonconventional NIR-RTP polymer alloy without significantly extensive conjugation. The PISP was synthesized via a catalyst-free multicomponent polymerization in air with high molecular weights (up to 41000 g/mol) and decent yields (up to 84%). Although lacking classical luminescent segments and largely extended conjugation, PISPs exhibit the clusterization-triggered cryogenic phosphorescence. More importantly, upon solution blending PISP with PS, the resultant polymer alloy shows a NIR-RTP emission up to 715 nm with a Stokes shift of 375 nm. This work will be of interest for developing luminescent materials for the optoelectronic devices, in vivo imaging, and flexible electronics.

Subject terms: Polymer synthesis, Polymers, Excited states

Most near-infrared room-temperature phosphorescent (NIR-RTP) materials are highly conjugated, requiring complex synthesis and resulting in poor processability. Here, the authors demonstrate the synthesis of a short-conjugated polymer via multicomponent spiropolymerization and blended it with polystyrene, achieving NIR-RTP polymers with good processability and high Stokes shift.

Introduction

Near-infrared room-temperature phosphorescent (NIR-RTP) materials are substances that exhibit phosphorescence in the near-infrared region (from 700 to 2500 nm) at ambient temperature after excitation1–3. NIR-RTP materials possess advantages such as strong penetration, low light loss, and negligible background interference. They hold considerable research and application value, particularly in fields like night vision equipment, high-performance optical devices, and in vivo imaging4,5. Classical organic NIR-RTP materials typically rely on extensive conjugation to efficiently absorb photons and emit phosphorescence6. However, introducing largely extended conjugation always results in aggregation-caused quenching, complex synthesis, poor processability, and high biological toxicity7,8. Very recently, a kind of room-temperature phosphorescent (RTP) material with limited or no conjugation has emerged, and this nonconventional phenomenon is named as clusterization-triggered room-temperature phosphorescence (CTRTP)9–12. In CTRTP, the aggregation of heteroatoms within clusters facilitates electron overlap and through-space conjugation, leading to the formation of singlet excitons under irradiation13–16. These singlet excitons then undergo intersystem crossing (ISC) to form triplet excitons, a process enhanced by heavy atoms and heteroatoms17–23. Strategies such as crystal engineering, supramolecular assembly, and host-guest doping are employed to stabilize and protect triplet excitons, leading to the efficient RTP emission24–31. Despite notable advancements, achieving long-wavelength, even near-infrared CTRTP still remains a significant challenge due to the inherent lack of extended conjugation9,14,15. Near-infrared clusterization-triggered room-temperature phosphorescent (NIR-CTRTP) polymeric materials combine the advantages of large Stokes shift, long emission lifetime, robust mechanical property, good processability, high tissue penetration, and low biotoxicity32–35. Their development holds significant value for both scientific research and industrial applications, and there is a pressing need to develop simple and efficient methods to construct NIR-CTRTP polymeric materials.

The intermolecular interactions can effectively modulate the energy gap and induce a redshift in the emission wavelength36–43. Recent advancements have shown that introducing through-space charge-transfer (TSCT) interactions can significantly enhance the long-wavelength fluorescence in clusteroluminogens44. This insight inspires us to investigate whether the polymer blending could be applied to achieve CTRTP while incorporating intermolecular charge-transfer interactions to extend its emission wavelengths to the near-infrared region. Multicomponent spiropolymerization (MCSP) is a powerful method to construct heteroatom-rich polymers with twisted spatial structures45,46. The resultant spiropolymers show the clusterization-triggered fluorescence originating from the through-space conjugation of heterospirocyclic structures47,48. According to the El-Sayed rule, the abundance of heteroatoms facilitates the generation of triplet excitons, which means that the heteroatom-rich spiropolymer is highly likely to emit the clusterization-triggered phosphorescence49. Moreover, the rigid and twisted spatial structures of spiropolymers can foster the formation of intermolecular interactions, which can be strategically utilized to enhance the emission intensity and extend the emission wavelength. Thus, by constructing polymer alloys containing spiropolymers, the NIR-CTRTP polymeric materials hold great potential for realization.

In this work, we develop a catalyst-free MCSP reaction and construct a class of spiropolymers, named as poly(iminofuran-spiro-pyrrolone)s (PISPs, Fig. 1a). Despite lacking traditional luminescent segments, PISPs exhibit the clusterization-triggered cryogenic phosphorescence. Upon solution blending PISPs with the commercially available rigid polymers, such as polystyrene (PS), poly(vinyl alcohol) (PVA), and poly(vinyl pyrrolidone) (PVP), the resulting polymer alloys display the desirable CTRTP, confirming that the polymer blending is an effective strategy for RTP emission (Fig. 1b). Notably, the PISP/PS alloy shows a NIR-CTRTP emission extending up to 715 nm, a result of the charge-transfer interaction between PISP and PS (Fig. 1b). The formation of the charge-transfer interaction is confirmed by the solid absorption result and leads to a significant Stokes shift of 375 nm. Further investigations show that high blend ratios, polymer matrix with large electrostatic potential difference, and PISPs with high weight-average molecular weight (Mw) and twisted spatial structures facilitate the realization of NIR-CTRTP emission. Thus, a polymerization reaction and polymer have been reported, the phosphorescence-emitting capability of the spiropolymer has been discovered, and a NIR-CTRTP material through the polymer blending strategy has been developed.

Fig. 1. Multicomponent spiropolymerization (MCSP) and room temperature phosphorescence (RTP) polymer alloy.

Fig. 1

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a MCSP between diisocyanide, activated alkyne, and bis-maleimide monomers. Chemical structures of diisocyanide monomer, activated alkyne monomer, bis-maleimide monomer, and spiropolymer P1-P8. b Formation of poly(iminofuran-spiro-pyrrolone) (PISP) cluster and poly(iminofuran-spiro-pyrrolone)/polystyrene (PISP/PS) alloy. Achievement of RTP and near-infrared RTP.

Results

Characterization and properties of PISPs

The polymerization kinetics of this MCSP reaction and proposed mechanism are discussed in detail in the Supplementary Information (Supplementary Figs. 1–3 and Supplementary Table 1). To confirm the chemical structures of polymers synthesized from MCSP, a model compound (MC) was prepared through the multicomponent reaction between the 1,4-diisocyanocyclohexane, diethyl acetylenedicarboxylate, and N-phenylmaleimide (Supplementary Figs. 4–6)50. Fig. 2a shows the 1H NMR spectrum of the MC, where all peaks are well-assigned. The hydrogen atoms with chemical shifts between 7.3 and 7.6 ppm originate from the aromatic ring of the MC. The signal labeled Ha1 corresponds to the hydrogen atoms on the cyclohexane ring, while Hb1 and Hc1 represent the alkyl hydrogens attached to the ester group. The peaks labeled Hd1 and He1 correspond to the hydrogen atoms on the double bonds. As shown in Fig. 2b, the 1H NMR spectrum of the resultant polymer closely resembles that of the MC, although the peaks are broader and less distinct because of the complex spatial structure and proton coupling within the polymer chains. Meanwhile, Fig. 2c presents the 13C NMR spectrum of the MC, which closely matches that of the resultant polymer (Fig. 2d). Notably, a key signal at 101 ppm, associated with spirocyclic carbon, appears after the multicomponent reaction and MCSP, directly confirming the formation of spirocyclic structures. Both the 1H and 13C NMR results indicate that the resultant polymer has a chemical structure highly consistent with the MC. The chemical structure of the prepared polymer is further validated by FT-IR spectroscopy. As shown in Figs. 2e, f, the peak of carbon-nitrogen double bond is observed at 1600 cm−1 and the carbon-oxygen single bond peak locates at 1095 cm−1. These features confirm the presence of the iminofuran structure within the MC and obtained polymer. In addition, the polymer backbone can be easily modified, and eight distinct variants of PISPs, designated as P1-P8, were synthesized using various combinations of diisocyanide, activated alkyne, and bis-maleimide monomers (Fig. 1a and Supplementary Table 1). Their chemical structures are also confirmed through the NMR and FT-IR results (Supplementary Figs. 7–21). The prepared polymers show good solubility and are readily soluble in a range of common organic solvents, including 1,4-dioxane, 1,2-dichloroethane, tetrahydrofuran (THF), dichloromethane (DCM), and toluene. Therefore, both NMR and FT-IR analyses validate the chemical structures of the resultant polymers, confirming the successful construction of PISPs through the MCSP.

Fig. 2. Structural characterizations of model compound (MC) and poly(iminofuran-spiro-pyrrolone).

Fig. 2

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a The 1H NMR spectrum of MC. b The 1H NMR spectrum of P1. c The 13C NMR spectrum of MC. d The 13C NMR spectrum of P1. e The FT-IR spectrum of MC. f The FT-IR spectrum of P1. The NMR spectra of MC were performed in deuterated dimethyl sulfoxide and the NMR spectra of P1 were recorded in deuterated chloroform.

The thermogravimetric analysis and differential scanning calorimetry (DSC) were performed to investigate the thermal stability of PISP. The decomposition temperature of P1, P2, and P3 range from 284 to 332 °C, and their carbon residues at 800 °C are higher than 30%, which could be owing to the presence of the amide and aromatic groups in their main chains (Supplementary Fig. 22). Meanwhile, no glass transition is observed in the DSC curves of P1, P2, and P3 in the range from 0 to 180 °C, which means that their glass transition temperatures (Tg) should be higher than 180 °C (Supplementary Fig. 23). The lack of glass transition observation is attributed to the rigid and twisted structure of the spiropolymer, combined with the extensive noncovalent interactions between polymer chains, which necessitate higher energy to induce movement in the polymer chain segments48. Therefore, the thermal analysis results demonstrate that the PISPs exhibit excellent thermal stability.

The photophysical properties of the resultant PISPs had been systematically investigated through the ultraviolet-visible (UV-Vis) and photoluminescence (PL) spectroscopy. Due to the absence of the conventional luminescent segments, P1 only exhibits obvious absorption below 260 nm in highly diluted solutions, attributed to the benzene rings and isolated carbonyl groups (Supplementary Fig. 24), and P1 is almost non-emissive when the concentration is equal to 5 × 10−5 M (Fig. 3a). Notably, as the concentration increases from 5 × 10−5 to 1 × 10−2 M, an absorption band emerges between 260 and 500 nm (Supplementary Fig. 24), and the PL intensity also improves from 260 to 2250 arbitrary units with the concentration increases from 5 × 10−5 to 5 × 10−3 M (Fig. 3a). Meanwhile, as shown in Fig. 3b, P1 also emits a 532 nm fluorescence in the solid state under the irradiation of 365 nm. This emission, termed as the clusterization-triggered fluorescence, arises from the through-space conjugation of oxygen, nitrogen, and carbonyl groups within the polymer clusters9,13,15. The presence of a polymer cluster is confirmed by the dynamic light scattering (DLS) measurement, which indicates a cluster size of approximately 295 nm, consistent with prior studies (Fig. 3c)48. In general, the clusterization-triggered fluorescence systems not only exhibit the aggregation-induced emission property but also the excitation-wavelength-dependent emission characteristic9,14,15. As shown in Fig. 3d, the P1 emission wavelength gradually shifts from 543 to 616 nm with increasing the excitation wavelength from 390 to 510 nm, further illustrating the clusterization-triggered fluorescence behavior of P1. In addition, not only P1 but also MC, P2, and P3 exhibit the concentration- and excitation-wavelength-dependent emission properties, demonstrating the effectiveness of MCSP in developing nonconventional luminescent materials (Supplementary Figs. 25 and 26).

Fig. 3. Photophysical properties of poly(iminofuran-spiro-pyrrolone).

Fig. 3

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a The photoluminescence (PL) curves of P1 with different concentrations in dichloromethane (DCM, excitation wavelength (λex) = 365 nm, and arb. units stands for arbitrary units). b The PL curves of P1 in the solid state (λex = 365 nm). Inset: the photo of solid P1 under the 365 nm irradiation. c The dynamic light scattering result of P1 with the concentration equal to 1 × 10−2 M in DCM. d The PL curves of P1 under different λex with the concentration equal to 1 × 10−3 M in DCM. e The steady-state and delayed PL curves of P1 in 2-methyl tetrahydrofuran (2-MeTHF) at 77 K (λex = 400 nm, delayed time = 0.05 ms, and concentration = 1 × 10−5 M). f The time-resolved phosphorescence decay curve of P1 in 2-MeTHF at 77 K (λex = 400 nm, concentration = 1 × 10−5 M, and τ stands for lifetime).

The PISPs are rich in the carbonyl groups and heteroatoms, and exhibit strong potential for phosphorescence as predicted by El-Sayed rules14,15,51. To assess their phosphorescence-emitting capabilities, the delayed luminescent properties of PISPs are further investigated. As shown in Fig. 3e, under the excitation at 400 nm, the cryogenic delayed emission of P1 shows a notable redshift from 520 to 568 nm compared with its steady-state emission. This redshift, along with a measured lifetime of 15.4 ms at 568 nm, confirms the phosphorescent nature of P1 emission (Fig. 3f). In addition, P1’s cryogenic delayed emission demonstrates the concentration- and excitation-wavelength-dependent characteristics, further supporting its clusterization-triggered phosphorescence behavior (Supplementary Fig. 27). The presence of heteroatoms and their lone-pair electrons enhance spin-orbit coupling (SOC) and facilitate ISC, which are critical for phosphorescence9,21,24. In addition to P1, P2 and P3 also show the clusterization-triggered cryogenic phosphorescence (Supplementary Fig. 28). Theoretical calculations on the repeating units of PISPs were carried out to further investigate the nature of clusterization-triggered cryogenic phosphorescence. As summarized in Supplementary Table 2 and Supplementary Fig. 29, effective ISC pathways are identified from S1 to Tn states, facilitating the generation of triplet excitons. Moreover, the repeating unit of P1 exhibits a SOC constant of 5.85 cm−1, that of P2 reaches 3.19 cm−1, and that of P3 attains 9.38 cm−1. These computational results suggest that PISPs possess the potential to undergo ISC and are capable of exhibiting phosphorescence. However, further attempts to observe the RTP emission of solid PISP were hindered by the instability of triplet excitons. These excitons are prone to being quenched by oxygen and dissipated through vibrations, both of which limit the efficiency of RTP emission21,24.

Photophysical properties of spiropolymer alloy

Our previous researches show that the polymers in a glassy state or those with high crystallinity can act as effective hosts, stabilizing triplet excitons from small molecules and enabling RTP emission52. In this study, to realize CTRTP, one of the classical and commercial rigid polymers, PS, was employed as the host matrix to provide a motion-restricted and protected environment to protect and stabilize the triplet excitons from PISPs. The polymer alloy was prepared via solution blending. Notably, under the excitation at 340 nm, the resultant P1/PS alloy exhibits a delayed emission at 530 nm with a lifetime of 1.21 ms at room temperature (RT, Fig. 4a, e). This result confirms that the polymer blending is an effective strategy for achieving CTRTP. The high chain motion activation energy of PS aids in stabilizing the triplet excitons from PISP and facilitates their radiative decay53. In addition, PS’s relatively low oxygen permeability helps prevent the quenching of triplet excitons53. By shielding the triplet excitons from the oxygen and restricting their motion, the polymer alloy demonstrates the desired CTRTP. Furthermore, the polymer blending strategy proves to be broadly applicable. As shown in Fig. 4, c, not only P1 but also P2 and P3 exhibit CTRTP when blended with PS. Specifically, P2/PS displays an RTP emission at 510 nm with a lifetime of 2.90 ms, and P3/PS also shows an RTP emission at 510 nm with a lifetime of 2.60 ms. Moreover, other rigid polymers, such as PVA and PVP, can serve as effective host matrices for achieving CTRTP. For instance, P1/PVA exhibits an RTP emission at 535 nm with a lifetime of 3.82 ms, while P1 blended with PVP shows an RTP emission at 505 nm with a lifetime of 1.28 ms (Fig. 4b, c). In contrast, when the PISPs are blended with the flexible polymers like polyisoprene (PI) and polybutadiene (PB), the CTRTP of the resultant polymer alloy is negligible (Supplementary Fig. 30). This phenomenon can be attributed to that the flexible polymers are less effective at restricting the motion of triplet excitons compared to the rigid polymers24,33. Control experiments demonstrate that PS, PVA, and PVP do not exhibit delayed emission, indicating that the observed phosphorescence of the polymer alloy primarily originates from the PISP rather than the host polymers (Supplementary Fig. 31). Therefore, these findings demonstrate that PISPs can effectively show RTP emission when blended with the rigid polymers, and that the polymer blending is a viable approach for realizing CTRTP.

Fig. 4. Photophysical properties of spiropolymer alloy.

Fig. 4

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a The steady-state and delayed photoluminescence (PL) curves of P1/polystyrene (P1/PS) with a blend ratio of 5% at room temperature (RT, excitation wavelength (λex) = 340 nm, and delayed time = 1 ms). b The delayed PL curves of P2/PS, P3/PS, P1/poly(vinyl alcohol) (P1/PVA), and P1/poly(vinyl pyrrolidone) (P1/PVP) with the blend ratio equal to 5% at RT (λex = 340 nm and delayed time = 1 ms). c The time-resolved phosphorescence decay curves of P2/PS, P3/PS, P1/PVA, and P1/PVP with the blend ratio equal to 5% at RT (λex = 340 nm and τ stands for lifetime). d The delayed PL curves of P1/PS with different blend ratios at RT (λex = 340 nm and delayed time = 1 ms). e The time-resolved phosphorescence decay curves of P1/PS with different blend ratios at RT (λex = 340 nm). f The confocal laser scanning microscopy images of 5% and 30% P1/PS in the different detection windows (λex = 405 nm and scale bar = 50 µm).

While the CTRTP has been successfully achieved through the polymer blending approach, the emission wavelength does not exhibit a significant bathochromic shift initially. Previous researches indicate that the benzene ring, as a classic electron donor group, can engage in charge-transfer interactions with the electron-deficient maleimide units during copolymerization with styrene54. Charge-transfer complexes formed between donors and acceptors often exhibit low energy level, which facilitate long-wavelength emission44. We hypothesize that the low blend ratio could result in weak charge-transfer interactions between the PISP and PS, which could account for the minimal bathochromic shift observed. To confirm this, a series of P1/PS alloys with different blend ratios were prepared, and their delayed PL spectra were collected, where the blend ratio 5% refers to the mass ratio of P1 to PS being 5%. As shown in Fig. 4d, increasing the blend ratio from 5% to 20%, 25%, and 30% leads to a notable redshift of the delayed emission from 530 to 560, 645, and 715 nm, respectively. The RTP nature can be further confirmed by the measurement of emission lifetime and the emission lifetimes of polymer alloys with different blend ratios are all in the millisecond range. As shown in Fig. 4e, the lifetime of 20% P1/PS at 555 nm is measured as 1.16 ms, 25% P1/PS at 645 nm has a lifetime of 1.28 ms, and 30% P1/PS at 715 nm shows a lifetime of 1.30 ms. Remarkably, the CTRTP of 30% P1/PS extends into the near-infrared region. To the best of our knowledge, such long-wavelength RTP emission has never been achieved among the nonconventional luminescent polymeric materials (Supplementary Fig. 32 and Supplementary Table 3)9,10,12,14,15,51,55–60. Further increasing the blend ratio does not affect the reproducibility of the NIR-RTP phenomenon. P1/PS with a blend ratio of 50% also exhibits CTRTP at 715 nm (Supplementary Fig. 33). The confocal laser scanning microscopy further confirms the observation of NIR-CTRTP emission. As shown in Fig. 4f, under radiation, both the 5% P1/PS and 30% P1/PS are emissive in the region ranging from 450 to 650 nm. No significant emission in the near-infrared region (650–750 nm) is detected in the 5% P1/PS, whereas the 30% P1/PS exhibits the pronounced emission. Therefore, these results demonstrate that the NIR-CTRTP emission can be achieved through the polymer blending strategy, and the high blending ratio is crucial for this achievement.

Mechanistic investigation and influencing factors of NIR-CTRTP emission

To elucidate the reason why the NIR-CTRTP emission is only evident at high blend ratios, the solid-state UV-Vis spectra of P1/PS with different blend ratios were collected. As shown in Fig. 5a, the absorption band with the peak located at 400 nm and the border extended to 550 nm can be attributed to the charge-transfer interaction between P1 and PS, and it gradually intensifies with blend ratios increasing. This result indicates that the significant charge-transfer interaction can only take place within the polymer alloy with high blend ratios. Based on these findings, we propose a reasonable explanation for this unique NIR-CTRTP emission. As illustrated in Fig. 5b, in the absence of PS, the PISP only exhibits the clusterization-triggered cryogenic phosphorescence. When the blend ratio is low, the PISP clusters are small and have low content, resulting in weak interactions between the PISP and PS. The RTP emission of the polymer alloy primarily arises from the through-space conjugation of electron-rich groups within the PISP cluster. As the blend ratio increases, the PISP cluster size and number grow, enhancing the charge-transfer interactions between the PISP and PS. At this point, the RTP emission of the polymer alloy mainly originates from the charge-transfer state between PISP and PS. Therefore, all of these results indicate that a high blend ratio facilitates the formation of the charge-transfer interactions, ultimately contributing to the achievement of the NIR-CTRTP emission.

Fig. 5. Mechanistic investigation and influencing factors of near-infrared clusterization-triggered room-temperature phosphorescence.

Fig. 5

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a The solid ultraviolet-visible absorption spectra of P1/polystyrene (P1/PS) with different blend ratios (arb. units stands for arbitrary units). b The proposed energy level diagram, where PISP stands for poly(iminofuran-spiro-pyrrolone), S0 stands for the ground state, S1 stands for the first singlet excited state, ISC stands for the intersystem crossing, Tn stands for the nth triplet excited state, and T1 stands for the first triplet excited state. c The delayed photoluminescence (PL) curves of P1/PS with different P1 molecular weights (blend ratio = 30%, excitation wavelength (λex) = 340 nm, and delayed time = 1 ms). d The delayed PL curves of P1/PS, P1/poly(vinyl alcohol) (P1/PVA), and P1/poly(vinyl pyrrolidone) (P1/PVP) (blend ratio = 30%, λex = 340 nm, and delayed time = 1 ms). e The delayed PL curves of P1/PS, P2/PS, and P3/PS (blend ratio = 30%, λex = 340 nm, and delayed time = 1 ms). f Glass transition temperature (Tg) of P1/PS alloy film with different blend ratios (Error bars represent standard deviation (SD). Data are presented as mean values ± SD. Each group of experiments was independently repeated three times (n = 3). For doping ratio = 0%, Tg is 104.5 ± 0.2 °C. For a doping ratio = 15%, Tg is 101.6 ± 0.5 °C. For doping ratio = 30%, Tg is 100.1 ± 0.7 °C). g The transmission electron microscope (TEM) images and particle size distribution results of 15% P1/PS (scale bar = 1 µm). h The TEM images and particle size distribution results of 30% P1/PS (scale bar = 1 µm).

To investigate the factors influencing the achievement of NIR-CTRTP emission, the delayed PL spectra of polymer alloys with different molecular weights, compositions, and blend ratios were collected. When the Mw of P1 increases from 2100 to 6000 and 8300 g/mol, the phosphorescence peak of the polymer alloys red-shifts from 512 to 595 and 715 nm, respectively (Fig. 5c). This phenomenon indicates that the molecular weight of P1 plays a crucial role in the formation of NIR-CTRTP emission, which could be attributed to the differences in the aggregation and clustering behavior of P1 with varying molecular weights. As shown in Fig. 5d and Supplementary Fig. 34, when increasing the blend ratio from 5% to 15% and 30%, the P1/PVA and P1/PVP do not show any bathochromic shift in their CTRTP. Reasons behind such phenomenon could be that these polymer matrixes lack electron donor segments and cannot form the charge-transfer interactions with P1.

In addition to the polymer matrix, the type of PISP guest is also crucial for achieving NIR-CTRTP emission. The RTP wavelengths of P2/PS and P3/PS remain nearly unchanged as the blend ratio increases (Fig. 5e and Supplementary Fig. 35), likely due to differences in the spatial configuration of PISP. Efficient TSCT interactions require close proximity between styrene and maleimide moieties. Planar conformations promote tight packing, suppressing micropore formation and preventing PS chains from penetrating into PISP clusters, thereby hindering TSCT interactions. P2 and P3, derived from para-substituted bismaleimide monomers, are expected to be more planar than P1, which originates from a meta-substituted monomer. To validate this assumption, the PL spectra of P8/PS were recorded. Like P1, P8/PS alloy exhibits a progressive red-shift in RTP emission with increasing blend ratios (Supplementary Fig. 36). Preliminary theoretical calculations reveal that the repeating unit dimer of P1 and P8 exhibit dihedral angles greater than 70°, suggesting twisted conformations that generate loose clusters favorable for TSCT interactions (Supplementary Fig. 37 and Supplementary Table 4). In contrast, dihedral angles of the repeating unit dimer of P2 and P3 are less than 30°, leading to planar conformations with compact clusters that suppress TSCT interactions (Supplementary Fig. 37 and Supplementary Table 4). Therefore, all of these results demonstrate that the polymer matrix with large electrostatic potential difference and the spiropolymer guest with high molecular weights and twisted spatial structure contribute to the achievement of NIR-CTRTP emission.

An incompatible polymer matrix can induce phase separation, facilitating the clusterization effect and thereby RTP emission. To investigate the compatibility and phase separation between P1 and PS, dynamic mechanical analysis (DMA) were conducted on P1/PS polymer alloys with different blend ratios. As the P1 content increases from 0% to 15% and 30%, the Tg of the polymer alloys remained within the range of 100–104 °C (Fig. 5f and Supplementary Fig. 38). The Tg of the polymer alloy is consistent with that of PS and is significantly lower than that of P1. Moreover, it remains unchanged with increasing P1 content. This observation indicates the poor compatibility between P1 and PS, which readily leads to phase separation. The phase separation and formation of polymer clusters were further confirmed by the transmission electron microscope (TEM) results. As shown in Supplementary Fig. 39, in the PS, there is no nanostructure present. When blending P1 with PS, the TEM images of the polymer alloys reveal numerous nanometer-sized spheres (Fig. 5g, h). The P1 contains various heteroatoms such as nitrogen and oxygen, which possess stronger electron absorption capabilities than the PS, allowing for their differentiation from the PS matrix in electron microscopy images. This distinction is further confirmed by energy-dispersive X-ray spectroscopy results. Both nitrogen and oxygen elements can be detected inside the nanostructure, indicating that the nanospheres are mainly composed of the spiropolymers (Supplementary Figs. 40 and 41). Conversely, the background of the TEM images lacks nitrogen element, suggesting that its primary component is the PS (Supplementary Figs. 42–44). In addition, as the blend ratio increases from 15% to 30%, the diameter of the nanostructure increases from 186 to 267 nm, further confirming the nanospheres is component by P1 (Fig. 5g, h). Moreover, the size of the P1 clusters observed by TEM is not only consistent with the size of the P1 clusters observed by DLS but also aligns with the sizes reported in other works48,61. Therefore, all of these results demonstrate that PISP clusters with a nanosphere morphology are well separated in the PS matrix.

Discussion

In summary, we have successfully developed a polymerization reaction and polymer, discovered the phosphorescence-emitting capability of the spiropolymer, and constructed a nonconventional NIR-RTP polymer alloy through blending spiropolymers with rigid polymers. Eight kinds of PISPs with sophisticated and elegant chemical structures are obtained through the catalyst-free MCSP of isocyanide, activated alkyne, and maleimide monomers. Despite lacking classical luminescent segments, the PISPs show the clusterization-triggered fluorescence and cryogenic phosphorescence, and after blending PISPs into the commercial and rigid polymers, such as PS, PVA, and PVP, the resultant polymer alloy displays the desirable CTRTP. More importantly, P1 forms the charge-transfer interactions with PS, leading to a NIR-RTP emission reaching up to 715 nm, which has never been achieved among the nonconventional luminescent polymeric materials. The nonconventional NIR-RTP polymer alloy avoids the aggregation-induced quenching and offers advantages such as simple synthesis, good processability, and ultra-large Stokes shift. This work demonstrates that the MCSP is a powerful method to construct organic functional materials with controllable structures and tunable properties, and the polymer blending is an efficient strategy to achieve NIR-RTP emission without significantly extensive conjugation. It’s highly anticipated that this line of research will open an avenue for designing nonconventional luminescent materials for optoelectronic devices, bio-medical imaging, and information technology.

Methods

Materials

Unless otherwise stated, all chemicals were obtained from commercial suppliers and used without further purification. Trans-1,4-diaminocyclohexane (98%), benzyltriethylammonium chloride (99%), 1,2-diaminobenzene (98%), maleic anhydride (99%), triethylamine (99%), dimethyl acetylenedicarboxylate (96%), diethyl acetylenedicarboxylate (98%), di-tert-butyl acetylenedicarboxylate (95%), N,N-1,4-phenylene bismaleimide (97%), N,N-1,3-phenylene bismaleimide (97%), pyromellitic diimide (97%), N-phenylmaleimide (99%), sodium hydroxide (NaOH, 99%), sodium bicarbonate (NaHCO3, 99%), sodium carbonate (Na2CO3, 99%), and anhydrous magnesium sulfate (MgSO4, 99%) were purchased from J&K, TCI, Energy Chemical, and Tianjin Zancheng Technology. PS (Mw = 95000 g/mol) was purchased from Aladdin. PVA (Mw = 95000 g/mol) was purchased from Sigma Aldrich. PVP (Mw = 58000 g/mol) was purchased from Thermo scientific. PI (Mw = 38000 g/mol) and PB (Mw = 20000 g/mol) were purchased from Adamas. Deuterated chloroform (CDCl3, 99%) and deuterated dimethyl sulfoxide (DMSO-d6, 99%) were purchased from Energy Chemical. Common solvents, such as chloroform (99%), acetone (99%), acetic anhydride (98%), dichloromethane (DCM, 99%), 1,2-dichloroethane (DCE, 99%), N,N-dimethylformamide (DMF, 99%), ethyl acetate (EA, 99%), petroleum ether (PE, analytical grade), tetrahydrofuran (THF, 99%), N-methylpyrrolidone (NMP, 99%), 2-methyl tetrahydrofuran (2-MeTHF, 99%), 1,4-dioxane (99%), and n-hexane (99%) were purchased from Beijing Chemworks.

Characterizations

The Mw and polymer dispersity index (Ð) of the resultant polymers were estimated on a Waters gel permeation chromatography system equipped with a Waters 1515 isocratic HPLC pump and Waters 2414 refractive index detector. The PS was utilized as standard, and THF was used as the eluent at a flow rate of 1.0 mL/min. 1H NMR and 13C NMR spectra were measured on a Bruker AV 400 spectrometer. Chemical shifts (δ) are reported in parts per million (ppm). Samples were prepared in deuterated solvents and referenced to residual non-deuterated solvent signals (CDCl3 @ 7.26 ppm in 1H NMR, CDCl3 @ 77.16 ppm in 13C NMR, DMSO-d6 @ 2.50 ppm in 1H NMR, DMSO-d6 @ 39.52 ppm in 13C NMR). FT-IR spectra were measured on a Bruker ALPHA spectrometer. The electrospray ionization mass spectrometry (ESI-MS) was performed by using a Finnigan BIFLEX III mass spectrometer. The high-resolution matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (HR-MALDI-TOF-MS) was performed by using a Bruker Solarix XR FTMS mass spectrometer and 2,5-dihydroxybenzoic acid matrix. Thermogravimetric analysis was carried out on a NETZSCH TG 209F3 at a heating rate of 10 °C/min under nitrogen flow. DSC was carried out on a DTG-60 & DSC-60 at a heating rate of 10 °C/min under nitrogen flow. UV-Vis absorption spectra were measured by Persee TU-1901. Fluorescence and phosphorescence spectra were measured by using a Hitachi F-7000 spectrophotometer and Nanolog FL3-2iHR. PL time-resolved phosphorescence decay curves were measured with a DeltaFlex ultrafast lifetime spectrofluorometer. The fluorescence and phosphorescence decay data were analyzed using DAS-6 Fluorescence Decay Analysis software with 2 exponential analysis programs. Sizes and distribution of the polymer cluster were performed by the DLS using Zetersizer Nano ZS980. The DMA, storage modulus, loss modulus, and damping factor of the composite specimens were measured as a function of temperature (from 25 to 150 °C) using a Mettler Toledo DMA/SDTA 1 + equipped with a small tension clamp fixture. The measurements were conducted at a frequency of 1 Hz and a heating rate of 10 °C/min. The typical sample size employed for the DMA tests was length × width × thickness (12 × 5 × 1 mm). TEM and energy dispersive X-ray microanalysis were both conducted with a JEM-2100 electron microscope. Samples with blend ratios of 0%, 15%, and 30% were diluted 100-fold, followed by spin coating on copper grids to form polymer alloys for subsequent analysis. Solid-state emission quantum yields were collected by using a FluoroMax-4 (Horiba Jobin Yvon, France) spectrofluorometer equipped with an integrated sphere.

Synthesis of diisocyanide monomers

Diisocyanide monomers (1,4-diisocyanocyclohexane, 1,4-bis(isocyanomethyl)benzene, and 1,4-diisocyano-2,5-dimethyl-benzene) were prepared according to similar procedures. The synthesis procedure of 1,4-diisocyanocyclohexane is given here as an example. Trans-1,4-diaminocyclohexane (5.70 g, 50 mmol), chloroform (8 mL, 100 mmol), benzyltriethylammonium chloride (0.23 g, 1 mmol), and DCE (20 mL) were successively added into a 100 mL round-bottom flask, and then stirred at RT for 5 min. A 50% (w/w) aqueous NaOH solution (20 mL) was prepared and then added dropwise into the flask in an ice-water bath. After the addition was complete, the flask was transferred to an oil bath, sealed with a rubber septum, and equipped with a balloon. The reaction was stirred at 40 °C for 12 h. After cooling to RT, the reaction mixture was washed with water (3 times) and separated. The combined aqueous phase was washed with DCM (3 times), and the combined organic phase was dried over MgSO4. The crude product was separated and purified by flash column chromatography under the eluent ratio of DCM/PE = 3/1. Finally, the white powder 1,4-diisocyanocyclohexane was obtained in a yield of 47%48.

Synthesis of N,N-1,2-phenylene bismaleimide

In a 250 mL three-neck round-bottom flask, 1,2-diaminobenzene (2.16 g, 0.02 mol) and acetone (80 mL) were added and stirred. A solution of maleic anhydride (4.31 g, 0.04 mol) dissolved in acetone (40 mL) was then added dropwise into the flask. The reaction mixture was stirred at 50 °C for 3 h and then heated to 80 °C. Triethylamine (12 mL), acetic anhydride (12 mL), and NaHCO3 (2.50 g, 0.03 mol) were added into the flask. The reaction mixture was then refluxed under a nitrogen atmosphere for 3 h. The resulting product was poured into ice-cold water. The product was washed multiple times with a 10% Na2CO3 aqueous solution until no acetic acid remained. Then, the product was washed with water and vacuum-dried. Finally, the light-yellow powder N,N-1,2-phenylene bismaleimide was obtained in a yield of 64%62.

Synthesis of MC

1,4-Diisocyanocyclohexane (130.0 mg, 1.0 mmol), diethyl acetylenedicarboxylate (340.0 mg, 1.0 mmol), N-phenylmaleimide (350.0 mg, 2.0 mmol), and 5 mL DCE were added to a 30 mL Schlenk tube. The reaction mixture was stirred at 100 °C for 24 h. After the reaction was finished, the organic layer was diluted by DCM, washed by water, and then dried over MgSO4. The MC was separated and obtained by flash column chromatography under the eluent ratio of EA/PE = 10/1 (Supplementary Figs. 4–6). MC: yellow powder in 43.0% yield. 1H NMR (400 MHz, DMSO-d6) δ 7.54-7.33 (m, 8H), 7.11-7.06 (m, 4H), 6.67 (d, 2H), 4.18 (t, 8H), 3.67 (s, 2H), 1.80-1.68 (m, 4H), 1.53-1.34 (m, 4H), 1.22-1.08 (m, 12H). 13C NMR (100 MHz, DMSO-d6) δ 169.16, 160.78, 159.15, 152.33, 144.91, 140.11, 137.22, 134.27, 129.85, 129.51, 128.54, 127.19, 101.67, 62.63, 62.56, 55.99, 40.63, 40.42, 40.21, 40.00, 39.79, 39.58, 39.38, 31.69, 31.53, 14.20, 14.03. ESI-MS (m/z): calcd for C44H44N4O12 + Na+ = 843.3 [M + Na]+, found = 843.3. HR-MALDI-TOF-MS (m/z): calcd for C44H44N4O12 + H+ = 821.3029 [M + H]+, found = 821.3037.

Polymerization procedure

Taking P1 as an example, to a 30 mL tube were added with 1,4-diisocyanocyclohexane (70.0 mg, 0.5 mmol), diethyl acetylenedicarboxylate (160.0 mg, 1.0 mmol), N,N-1,3-phenylene bismaleimide (130.0 mg, 0.5 mmol), and 5 mL of 1,4-dioxane. The reaction mixture was stirred under an air atmosphere at 100 °C for 12 h. After the polymerization was finished, the mixture was cooled to RT, and poured into 200 mL of n-hexane under vigorous stirring. Then, the precipitate was filtered, and washed with n-hexane. To ensure the purity, P1 was precipitated twice in n-hexane and dried to a constant weight in a vacuum at 50 °C. Other polymerization reactions have the same procedure in different conditions (Supplementary Table 1).

Preparation of polymer alloy

Taking the P1/PS alloy as an example. Firstly, the polymer guest P1 is weighed in varying amounts (1.0 mg, 3.0 mg, 4.0 mg, 5.0 mg, and 6.0 mg) and combined with a constant quantity of the polymer host PS (20.0 mg). These mixtures are then dissolved in NMP (2 mL) at RT with overnight stirring until complete dissolution. Subsequently, 300 μL of each homogeneous mixture is extracted using a micropipette and deposited onto 1 cm × 1 cm quartz sheet. The substrates are then placed in a vacuum oven at 80 °C overnight to remove the solvent. This process results in the formation of a doped polymer alloy with guest-host doping ratios of 5%, 15%, 20%, 25%, and 30%, respectively. The Mw of polymer guest P1, P2, P3, and P8 in the polymer alloy are 8300, 9200, 41000, and 4200 g/mol, respectively. The Đ of polymer guest P1, P2, P3, and P8 are 3.1, 2.9, 3.1, and 2.0, respectively.

The theoretical calculation method

The repeating unit monomer and dimer structures of P1, P2, P3, and P8 were optimized at the CAM-B3LYP/6-31 G(d) level with the density functional theory (DFT) method. The excited electronic structures of these structures were calculated at the PBE0/def2-SV(P) level with the time-dependent density functional theory (TD-DFT) method. The SOC matrix elements were calculated with the ORCA 4.2.1 program using the SOME method based on the excited-state wave functions obtained from TD-DFT calculations. The dihedral angles were subsequently computed with the Mercury crystal-analysis software.

Supplementary information

Supplementary Information (3.8MB, pdf)
Supplementary Data 1 (36.7KB, xlsx)
Transparent Peer Review file (4.6MB, pdf)

Source data

Source Data (13.1MB, xlsx)

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (52473290 and 22222501 received by Z.C.; 22401017 received by Y.D.; 52403006 received by Y.R.), the Beijing Natural Science Foundation (2232022 received by Z.C.; 2242060 received by P.S.), the BIT Research Fund Program for Young Scholars (XSQD6120220239 received by P.S.). and the Huaibei Normal University 2025 Key Laboratory of the Ministry of Education Independent Research Project (KLGPSCA202503 received by Y.R.).

Author contributions

Z.C., Y.D., and P.S. designed the research work and revised the manuscript. Y.R., Y.Zhang, H.S., W.Y., and L.Z. synthesized and prepared the materials. Y.R., Y. Zhang, W.D., and Y. Zhao carried out photophysical property measurements. Y.R., Z.C., and P.S. wrote the manuscript. Y.D., Z.C., P.S., B.T., J.Z., J.S., and T.W. edited the manuscript. All authors discussed the results and commented on the manuscript.

Peer review

Peer review information

Nature Communications thanks Youhong Tang and the other anonymous reviewers for their contribution to the peer review of this work. A peer review file is available.

Data availability

The data that support the findings of this study are available in the article and the Supplementary Information, or are available from the corresponding author upon request. Source data are provided in this paper.

Competing interests

The authors declare no competing interests.

Footnotes

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

These authors contributed equally: Yue Ren, Yongfeng Zhang.

Contributor Information

Peng Sun, Email: sunpeng@bit.edu.cn.

Zhengxu Cai, Email: caizx@bit.edu.cn.

Supplementary information

The online version contains supplementary material available at 10.1038/s41467-025-66035-w.

References

  • 1.Chang, B. et al. A phosphorescent probe for in vivo imaging in the second near-infrared window. Nat. Biomed. Eng.6, 629–639 (2021). [DOI] [PubMed] [Google Scholar]
  • 2.Liu, D. et al. Highly efficient circularly polarized near-infrared phosphorescence in both solution and aggregate. Nat. Photonics18, 1276–1284 (2024). [Google Scholar]
  • 3.Yan, Z. A., Yin, C., Tian, H. & Ma, X. Near-infrared room-temperature phosphorescence from monocyclic luminophores. Angew. Chem. Int. Ed.64, e202417397 (2025). [DOI] [PubMed] [Google Scholar]
  • 4.Dang, Q. et al. Room-temperature phosphorescence resonance energy transfer for construction of near-infrared afterglow imaging agents. Adv. Mater.32, e2006752 (2020). [DOI] [PubMed] [Google Scholar]
  • 5.Tu, L., Xie, Y., Li, Z. & Tang, B. Aggregation-induced emission: Red and near-infrared organic light-emitting diodes. SmartMat2, 326–346 (2021). [Google Scholar]
  • 6.Xiao, F. M. et al. Guest-host doped strategy for constructing ultralong-lifetime near-infrared organic phosphorescence materials for bioimaging. Nat. Commun.13, 186 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 7.Mei, J. et al. Aggregation-induced emission: the whole is more brilliant than the parts. Adv. Mater.26, 5429–5479 (2014). [DOI] [PubMed] [Google Scholar]
  • 8.Gao, M. et al. A new insight into aggregation structure of organic solids and its relationship to room-temperature phosphorescence effect. Aggregate5, e462 (2023). [Google Scholar]
  • 9.Tang, S. et al. Nonconventional luminophores: characteristics, advancements and perspectives. Chem. Soc. Rev.50, 12616–12655 (2021). [DOI] [PubMed] [Google Scholar]
  • 10.Ju, H. Q. et al. Polymerization-induced crystallization of dopant molecules: an efficient strategy for room-temperature phosphorescence of hydrogels. J. Am. Chem. Soc.145, 3763–3773 (2023). [DOI] [PubMed] [Google Scholar]
  • 11.Gao, Q. et al. Fully exploiting clusterization-triggered room temperature phosphorescence of cellulose by stepwise rigidification for long-lived and excitation wavelength-dependent afterglows. Adv. Funct. Mater.34, 2403977 (2024). [Google Scholar]
  • 12.Shi, M. et al. Confinement-modulated clusterization-triggered time-dependent phosphorescence color from Xylan-carbonized polymer dots. J. Am. Chem. Soc.146, 1294–1304 (2023). [DOI] [PubMed] [Google Scholar]
  • 13.Ren, Y. et al. Clusterization-triggered color-tunable room-temperature phosphorescence from 1,4-dihydropyridine-based polymers. J. Am. Chem. Soc.144, 1361–1369 (2022). [DOI] [PubMed] [Google Scholar]
  • 14.Luo, X. et al. Room-temperature phosphorescent materials derived from natural resources. Nat. Rev. Chem.7, 800–812 (2023). [DOI] [PubMed] [Google Scholar]
  • 15.Yang, T., Li, Y., Zhao, Z. & Yuan, W. Z. Clustering-triggered phosphorescence of nonconventional luminophores. Sci. China Chem.66, 367–387 (2022). [Google Scholar]
  • 16.You, J. et al. Aggregation-regulated room-temperature phosphorescence materials with multi-mode emission, adjustable excitation-dependence and visible-light excitation. Nat. Commun.14, 4163 (2023). [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 17.Wang, Z. et al. Recent advances in organic room-temperature phosphorescence of heteroatom (B/S/P)-containing chromophores. CCS Chem.5, 292–309 (2023). [Google Scholar]
  • 18.Zhu, T., Yang, T., Zhang, Q. & Yuan, W. Z. Clustering and halogen effects enabled red/near-infrared room temperature phosphorescence from aliphatic cyclic imides. Nat. Commun.13, 2658 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 19.Cheng, Z. et al. Efficient purely organic room-temperature phosphorescence from selenium-containing conjugated polymers for signal-amplified oxygen detection. Macromolecules56, 2972–2979 (2023). [Google Scholar]
  • 20.Su, H. et al. Functional roles of polymers in room-temperature phosphorescent materials: modulation of intersystem crossing, air sensitivity and biological activity. Angew. Chem. Int. Ed.62, e202218712 (2023). [DOI] [PubMed] [Google Scholar]
  • 21.Yang, X., Waterhouse, G. I. N., Lu, S. & Yu, J. Recent advances in the design of afterglow materials: mechanisms, structural regulation strategies and applications. Chem. Soc. Rev.52, 8005–8058 (2023). [DOI] [PubMed] [Google Scholar]
  • 22.Cao, Y. et al. Multi-functional integration of phosphor, initiator, and crosslinker for the photo-polymerization of flexible phosphorescent polymer gels. Angew. Chem. Int. Ed.63, e202401331 (2024). [DOI] [PubMed] [Google Scholar]
  • 23.Zhou, L. et al. Achieving efficient dark blue room-temperature phosphorescence with ultra-wide range tunable lifetime. Angew. Chem. Int. Ed.63, e202403773 (2024). [DOI] [PubMed] [Google Scholar]
  • 24.Zhao, W., He, Z. & Tang, B. Z. Room-temperature phosphorescence from organic aggregates. Nat. Rev. Mater.5, 869–885 (2020). [Google Scholar]
  • 25.Dai, W. et al. Halogen bonding: a new platform for achieving multi-stimuli-responsive persistent phosphorescence. Angew. Chem. Int. Ed.61, e202200236 (2022). [DOI] [PubMed] [Google Scholar]
  • 26.Chen, B., Huang, W. & Zhang, G. Observation of Chiral-selective room-temperature phosphorescence enhancement via chirality-dependent energy transfer. Nat. Commun.14, 1514 (2023). [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 27.Hamzehpoor, E. et al. Efficient room-temperature phosphorescence of covalent organic frameworks through covalent halogen doping. Nat. Chem.15, 83–90 (2023). [DOI] [PubMed] [Google Scholar]
  • 28.Wei, J. et al. Conformation-dependent dynamic organic phosphorescence through thermal energy driven molecular rotations. Nat. Commun.14, 627 (2023). [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 29.Feng, R. et al. Transitioning room-temperature phosphorescence from solid states to aqueous phases via a cyclic peptide-based supramolecular scaffold. Angew. Chem. Int. Ed.64, e202421729 (2024). [DOI] [PubMed] [Google Scholar]
  • 30.Zhao, Y. et al. Fused-ring pyrrole-based near-infrared emissive organic RTP material for persistent afterglow bioimaging. Angew. Chem. Int. Ed.63, e202317431 (2024). [DOI] [PubMed] [Google Scholar]
  • 31.Zhang, J. et al. Highly bright pure room temperature phosphorescence for circularly polarized organic hyperafterglow. Adv. Mater.37, 2500953 (2025). [DOI] [PubMed] [Google Scholar]
  • 32.Sun, P., Qin, B., Xu, J.-F. & Zhang, X. Supramonomers for controllable supramolecular polymerization and renewable supramolecular polymeric materials. Prog. Polym. Sci.124, 101486 (2022). [Google Scholar]
  • 33.Dou, X. et al. Advances in polymer-based organic room-temperature phosphorescence materials. Adv. Funct. Mater.34, 2314069 (2024). [Google Scholar]
  • 34.Liu, J. et al. Circularly polarized organic ultralong room-temperature phosphorescence with a high dissymmetry factor in chiral helical superstructures. Adv. Mater.36, 2306834 (2023). [DOI] [PubMed] [Google Scholar]
  • 35.Liu, J. et al. Dynamically modulating the dissymmetry factor of circularly polarized organic ultralong room-temperature phosphorescence from soft helical superstructures. Angew. Chem. Int. Ed.63, e202319536 (2024). [DOI] [PubMed] [Google Scholar]
  • 36.Zhu, W. et al. Revealing the charge-transfer interactions in self-assembled organic cocrystals: two-dimensional photonic Applications. Angew. Chem. Int. Ed.54, 6785–6789 (2015). [DOI] [PubMed] [Google Scholar]
  • 37.Kabe, R. & Adachi, C. Organic long persistent luminescence. Nature550, 384–387 (2017). [DOI] [PubMed] [Google Scholar]
  • 38.Shao, S. & Wang, L. Through-space charge transfer polymers for solution-processed organic light-emitting diodes. Aggregate1, 45–56 (2020). [Google Scholar]
  • 39.Zhang, J. et al. Secondary through-space interactions facilitated single-molecule white-light emission from clusteroluminogens. Nat. Commun.13, 3492 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 40.Xiong, Z. et al. Controllable secondary through-space interaction and clusteroluminescence. CCS Chem.5, 2832–2844 (2023). [Google Scholar]
  • 41.Zhang, Z. et al. NIR Clusteroluminescence of non-conjugated phenolic resins enabled by through-space interactions. Angew. Chem. Int. Ed.62, e202306762 (2023). [DOI] [PubMed] [Google Scholar]
  • 42.Wang, Y., Feng, R., Yu, Y. & Song, Q. Supramolecular thermally activateddelayedfluorescence materials via through-space charge transfer. CCS Chem.6, 1165–1173 (2024). [Google Scholar]
  • 43.Yin, Z. et al. Cocrystallization-induced red ultralong organic phosphorescence. Angew. Chem. Int. Ed.64, e202417868 (2025). [DOI] [PubMed] [Google Scholar]
  • 44.Chu, B. et al. Enabling nonconjugated polyesters emit full-spectrum fluorescence from blue to near-infrared. Nat. Commun.15, 366 (2024). [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 45.Zhu, G. et al. Multicomponent spiropolymerization of diisocyanides, activated alkynes, and bis-anhydrides. Macromolecules55, 6150–6159 (2022). [Google Scholar]
  • 46.Zhu, L.-J. et al. Catalyst-free four-component spiropolymerization for the construction of spirocopolymers with tunable photophysical properties. Chin. J. Polym. Sci.41, 1525–1532 (2023). [Google Scholar]
  • 47.Liu, P. et al. MDM2-Associated clusterization-triggered emission and apoptosis induction effectuated by a theranostic spiropolymer. Angew. Chem. Int. Ed.59, 8435–8439 (2020). [DOI] [PubMed] [Google Scholar]
  • 48.Zhu, G. et al. Construction, characterization, and properties of poly(iminofuran-spiro-oxindole)s through catalyst-free multicomponent spiropolymerization of diisocyanides, activated alkynes, and bis-isatins. Macromolecules56, 10101–10110 (2023). [Google Scholar]
  • 49.Zhang, T. et al. Molecular engineering for metal-free amorphous materials with room-temperature phosphorescence. Angew. Chem. Int. Ed.59, 11206–11216 (2020). [DOI] [PubMed] [Google Scholar]
  • 50.Adib, M., Moghimi, S., Sayahi, M. H. & Bijanzadeh, H. R. One-pot three-component synthesis of 2-(Alkylimino)-7-oxo-1-oxa-6-azaspiro[4.4]nona-3,8-diene-3,4-dicarboxylates. Helv. Chim. Acta92, 944–949 (2009). [Google Scholar]
  • 51.Xu, L. Unconventional aggregation-induced emission property with clusteroluminescence mechanism from natural compounds and applications. Coord. Chem. Rev.519, 216094 (2024). [Google Scholar]
  • 52.Zhang, Y. et al. Microwave-responsive flexible room-temperature phosphorescence materials based on poly(vinylidene fluoride). Polym. Angew. Chem. Int. Ed.62, e202314273 (2023). [DOI] [PubMed] [Google Scholar]
  • 53.Qiu, L. et al. Room-temperature phosphorescence induced by heterogeneous polymer matrixes. Macromolecules57, 2679–2686 (2024). [Google Scholar]
  • 54.Shan, G.-R. S., Huang, Z.-M. H., Weng, Z.-X. W. & Pan, Z.-R. a-new-model-of-mechanism-and-treatment-of-kinetics-for-styrene-n-phenylmaleimide-copolymerization. Macromolecules30, 1279 (1997). [Google Scholar]
  • 55.Zhou, Q. et al. Clustering-triggered emission of nonconjugated polyacrylonitrile. Small12, 6586–6592 (2016). [DOI] [PubMed] [Google Scholar]
  • 56.Chen, X. et al. Aggregation-induced dual emission and unusual luminescence beyond excimer emission of poly(ethylene terephthalate). Macromolecules51, 9035–9042 (2018). [Google Scholar]
  • 57.Wang, Q. et al. Reevaluating protein photoluminescence: remarkable visible luminescence upon concentration and insight into the emission mechanism. Angew. Chem. Int. Ed.58, 12667–12673 (2019). [DOI] [PubMed] [Google Scholar]
  • 58.Chen, K. et al. Long-lived room temperature phosphorescence from amorphous non-traditional intrinsic clusteroluminescence polymers. J. Mater. Chem. C10, 16420–16429 (2022). [Google Scholar]
  • 59.Shi, C. Y. et al. A dynamic supramolecular H-bonding network with orthogonally tunable clusteroluminescence. Angew. Chem. Int. Ed.62, e202214422 (2023). [DOI] [PubMed] [Google Scholar]
  • 60.Wang, Y.-L. et al. Hydrogen bonding-induced oxygen clusters and long-lived room temperature phosphorescence from amorphous polyols. Chin. Chem. Lett.34, 107684 (2023). [Google Scholar]
  • 61.He, B. et al. Clusteroluminescence from cluster excitons in small heterocyclics free of aromatic rings. Adv. Sci.8, 2004299 (2021). [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 62.Kaliavaradhan, K. et al. Synthesis and characterization of various phenylene diamine-based bismaleimide-containing phthalonitrile resins. Polym. Bull.73, 1921–1938 (2015). [Google Scholar]

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Data Availability Statement

The data that support the findings of this study are available in the article and the Supplementary Information, or are available from the corresponding author upon request. Source data are provided in this paper.

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