Functional Roles of Polymers in Room‐Temperature Phosphorescent Materials: Modulation of Intersystem Crossing, Air Sensitivity and Biological Activity

Su, Hao; Hu, Kan; Huang, Wenhuan; Wang, Tao; Zhang, Xiaolong; Chen, Biao; Miao, Hui; Zhang, Xuepeng; Zhang, Guoqing

doi:10.1002/anie.202218712

Cited by 42 publications

(30 citation statements)

References 64 publications

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“…In 2023, Zhang et al developed four copolymers, Dye1- co -PS, Dye1- co -PMMA, Dye1- co -PVP, and Dye1- co -PQAS, using a triphenylamine derivative (Dye1) as the luminophore to investigate more function of polymer (Figure b). All four copolymers exhibit obvious RTP afterglow, but with differences in wavelengths and intensities.…”

Section: Construction Of Polymer-based Rtp Systemsmentioning

confidence: 99%

Recent Advances of Pure Organic Room Temperature Phosphorescence Based on Functional Polymers

Ding,

Ma,

Tian

2023

Acc. Mater. Res.

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Conspectus The phosphorescence is produced by the radiative transition of the excited triplet state which is generated by the intersystem crossing (ISC) from the excited singlet state. Compared with fluorescence, it has a longer luminescence lifetime and larger Stokes shift, so phosphorescent materials have great application value in fields such as displays, anticounterfeiting, and imaging. But due to the low ISC rate of organic molecules, the slow radiative transition rate of the triplet state, and the large nonradiative energy loss caused by molecular vibration, pure organic room temperature phosphorescence (RTP) is usually difficult to obtain. Among the most widely used strategies including crystal assembly, polymerization, and host–guest encapsulation, the polymerization strategy based on rigid polymers has achieved great success and widespread attention due to their easy processing and excellent luminescence performance. The main function of polymers is to fix the luminophore into the matrix and suppress the energy loss of the triplet state caused by nonradiative transitions and oxygen quenching. That is, polymers provide a rigid microenvironment necessary for the RTP, although some polymers are flexible and stretchable. Conventional polymers have limited interaction with luminophores and do not have the function of promoting triplet states. Therefore, the high RTP quantum yield depends more on the structural design of luminophores. By modification of the structure, functionalized polymers can be endowed with the ability to regulate the singlet and triplet energy levels of luminophores, enhance ISC, and increase the quantum yield of RTP. The selection of functionalized polymers also enriches the diverse properties of RTP materials. This Account summarizes the latest research progress in the field of polymer-based RTP and RTP enhancement by functionalized polymers. Luminophores are used to construct RTP systems by doping, covalent linking, or supramolecular interactions with polymers such as PAA, PMMA, PVA, and PAM. To further strengthen polymer rigidity, secondary processing has been successfully employed to synergistically suppress nonradioactivation and enhance RTP performance, such as hydrogen bonding bridges, host–guest encapsulation, and cross-linking. The function of polymers is no longer limited to suppressing nonradiative transitions but also includes enhancing the yield of triplet states and generating special luminescence phenomena. A few functionalized polymers are specially designed to utilize external heavy atom effects, dipole–dipole interactions, and electrostatic and diffusion interactions with the luminophores to promote the ISC rate. Due to the diversification and functionalization of polymers, RTP systems were developed with various special luminescence phenomena such as photoactivation, excitation wavelength dependence, photochromism, circularly polarized RTP, and stimulus-response. We hope the summarized functions and development trends of polymers in RTP systems can provide helpful gui...

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Section: Construction Of Polymer-based Rtp Systemsmentioning

confidence: 99%

Recent Advances of Pure Organic Room Temperature Phosphorescence Based on Functional Polymers

Ding,

Ma,

Tian

2023

Acc. Mater. Res.

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“…Organic room‐temperature phosphorescence (RTP) materials have attracted immense attention due to their peculiar photophysical process and potential applications in advanced printable and writable security inks, [ 1‐4 ] high‐resolution bioimaging, [ 5‐7 ] microenvironment oxygen visual sensing and quantitative detection. [ 8‐11 ] Several attempts have been made to develop high‐performance RTP materials, including the introduction of heavy atoms or halogen/hydrogen bonding, [ 12‐17 ] doping in a rigid matrix, [ 18‐26 ] construction of metal‐organic frameworks, [ 27‐28 ] and ionic‐π interactions. [ 29‐31 ] However, limited RTP materials with long emission wavelengths are reported due to the lack of a preparation strategy.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Organic Host‐Guest Materials with Bright Red Room‐Temperature Phosphorescence for Persistent Bioimaging^†

Zhao

Dai

et al. 2023

Chin. J. Chem.

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Comprehensive Summary Organic room‐temperature phosphorescence (RTP) materials have attracted immense attention in bioimaging due to their long emission lifetime and large Stokes shift. RTP materials with long emission wavelength can improve the penetration depth for bioimaging. However, the design of red persistent RTP materials is still challenging. In this study, a fused‐ring structure has been proposed to effectively decrease the triplet energy level, thus extending the emission wavelength of phosphorescence. In addition, the fused‐ring structure exhibits a high molar extinction coefficient (ɛ) and high luminescence efficiency due to the rigid structure. A new class of crystalline hosts (iminodibenzyl, IDB) are developed to stabilize the triplet excitons that are generated from the fused‐ring molecules. The maximum RTP wavelength of doping materials can reach 635 nm with a lifetime of 9.35 ms. Water‐disperse nanoparticles are successfully prepared for in vivo time‐resolved bioimaging, which eliminates the background fluorescence interference from biological tissues. These reveal a delicate design strategy for the construction of long‐wavelength emissive RTP materials for high‐resolution bioimaging.

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“…3 (π, π*) transition is another important module for boosting ISC and RTP based on the El-Sayed's rule; [33][34] therefore, functional groups containing out-of-plane electronic transitions such as carbonyls or nitrates are routinely attached to aromatic rings for this purpose. [35][36] Among all organic luminophores, polyaromatic hydrocarbons (PAHs) such as pyrene, despite their natural abundancy in fossil fuels, are yet to be tapped for efficient RTP, for an apparent lack of any significant means to increase SOC or reduce ΔE ST . [37] As a result, extrinsic stimuli must be introduced to turn PAHs into efficient RTP emitters.…”

Section: Introductionmentioning

confidence: 99%

Disorder‐Enhanced Charge‐Transfer‐Mediated Room‐Temperature Phosphorescence in Polymer Media

Cheng,

Su,

et al. 2023

Angew Chem Int Ed

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Room‐temperature phosphorescence (RTP) polymers have important applications for biological imaging, oxygen sensing, data encryption, and photodynamic therapy. Despite the many advantages polymeric materials offer such as great control over gas permeability and processing flexibility, disorder is traditionally considered as an intrinsic negative impact on the efficiency for embedded RTP luminophores, as various allowed thermal motions could quench the emitting states. However, we propose that such disorder‐enabled freedoms of microscopic motions can be beneficial for charge‐transfer‐mediated RTP, which is facilitated by molecular conformational changes among different electronic transition states. Using the “classic” pyrene‐aniline excimer as an example, we demonstrate the mutual enhancement of red/near‐infrared and green RTP emissions from the pyrene and aniline moieties, respectively, upon doping of the aniline polymer with trace pyrene derivatives. In comparison, a pyrene‐doped crystal formed with the same aniline structure exhibits only charge‐transfer fluorescence with no red or green RTP observed, suggesting that order suppresses the RTP channels. The proposed polymerization strategy may be used as a unified method to generate multi‐emissive polymeric RTP materials from a vast pool of known and unknown exciplexes and charge‐transfer complexes.

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Functional Roles of Polymers in Room‐Temperature Phosphorescent Materials: Modulation of Intersystem Crossing, Air Sensitivity and Biological Activity

Cited by 42 publications

References 64 publications

Recent Advances of Pure Organic Room Temperature Phosphorescence Based on Functional Polymers

Recent Advances of Pure Organic Room Temperature Phosphorescence Based on Functional Polymers

Organic Host‐Guest Materials with Bright Red Room‐Temperature Phosphorescence for Persistent Bioimaging^†

Disorder‐Enhanced Charge‐Transfer‐Mediated Room‐Temperature Phosphorescence in Polymer Media

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Functional Roles of Polymers in Room‐Temperature Phosphorescent Materials: Modulation of Intersystem Crossing, Air Sensitivity and Biological Activity

Cited by 42 publications

References 64 publications

Recent Advances of Pure Organic Room Temperature Phosphorescence Based on Functional Polymers

Recent Advances of Pure Organic Room Temperature Phosphorescence Based on Functional Polymers

Organic Host‐Guest Materials with Bright Red Room‐Temperature Phosphorescence for Persistent Bioimaging†

Disorder‐Enhanced Charge‐Transfer‐Mediated Room‐Temperature Phosphorescence in Polymer Media

Contact Info

Product

Resources

About

Organic Host‐Guest Materials with Bright Red Room‐Temperature Phosphorescence for Persistent Bioimaging^†