Circularly Polarized Organic Room Temperature Phosphorescence from Amorphous Copolymers

Gu, Long; Ye, Wenpeng; Liang, Xiao; Lv, Anqi; Ma, Huili; Singh, Manjeet; Jia, Wenyong; Shen, Zhaocun; Guo, Yi; Gao, Ya‐Ru; Chen, Hongzhong; Wang, Dongdong; Wu, Yinglong; Liu, Jiawei; Wang, Hou; Zheng, You‐Xuan; An, Zhongfu; Huang, Wei; Zhao, Yanli

doi:10.1021/jacs.1c08118

Cited by 151 publications

(97 citation statements)

References 45 publications

(58 reference statements)

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“…For instance, Kawai and co-workers shed light on the naked-eye-detectable CPL using helicates with a g lum up to 1.25 . In spite of this work, most studies on CPL focus on the fundamental investigation without applications due to the limited g lum . − ,, Therefore, in the present work, the g lum of circularly polarized phosphorescence ranges from 1 to 5 × 10 –3 . Without a spectrometer, it is hard to recognize the circularly polarized phosphorescence using the naked eye.…”

Section: Resultsmentioning

confidence: 85%

Ultraviolet Light Detectable Circularly Polarized Room Temperature Phosphorescence in Chiral Naphthalimide Self-Assemblies

Liang

Hao

et al. 2021

ACS Nano

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The combination of circularly polarized luminescence (CPL) and pure-organic room temperature phosphorescence (RTP) potentially facilitates the construction of organic chiroptical optoelectronics and display materials, which however are challenging to use in realizing smart control of luminescent colors and switchable chiroptical properties. Here, we show a host−guest strategy to fabricate color-tunable RTP-based circularly polarized phosphorescence. Napthalimides were conjugated directly to chiral segments, of which supramolecular chirality and CPL activities in solid-states could be triggered by substituting bromine atoms on amines. Introducing tetracyanobenzene as an achiral host matrix via simple grinding would allow for the intersystem crossing to trigger red RTP and corresponding CPL by excitation lower than 320 nm, with a large Stokes shift more than 300 nm. The critical excitation wavelength of the RTP switch is determined by the absorbance of tetracyanobenzene. When the excitation wavelength was larger than 320 nm, blue fluorescence dominated with turned off RTP and CPL. The excitation wavelength-dependent RTP and CPL switch allows for detecting ultraviolet (UV) light, showing distinguishable red−blue luminescent color transition, accompanied by on/off RTP. Changing the host matrix from tetracyanobenzene to tricyanobenzene or dicyanobenzene could adjust the critical detecting wavelength limit from 320 to 300 nm. This work establishes a strategy to realize color-tunable, UV light detectable RTP and CPL under smart control.

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Section: Resultsmentioning

confidence: 85%

Ultraviolet Light Detectable Circularly Polarized Room Temperature Phosphorescence in Chiral Naphthalimide Self-Assemblies

Liang

Hao

et al. 2021

ACS Nano

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“…Moreover, novel RTP materials with CPL characteristics have rarely been obtained [14] . To date, only several successful examples with long‐lived room‐temperature circularly‐polarized phosphorescence have been reported through the restriction of motions of chiral luminophores in the crystalline state, [14b,c] rigid host matrix, [14a, 15] chiral clusterization, [16] and polymer matrix [14e, 17] . However, either luminescence efficiency or dissymmetry factor is found far from satisfactory after a brief summary in Figure S1.…”

Section: Methodsmentioning

confidence: 99%

Strong Circularly‐Polarized Room‐Temperature Phosphorescence from a Feasibly Separable Scaffold of Bidibenzo[b,d]furan with Locked Axial Chirality

Huang

Liang

et al. 2022

Angewandte Chemie

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Figure 4. Top: Normalized prompt and delayed (1 ms) PL spectra; middle: CPL spectra; bottom: g lum of a) as-prepared and b) treated PVA films with doped (R)-1 (w (R)-1 :w PVA = 1 : 600) at room temperature with 290 nm excitation. Phosphorescent decay curves of c) as-prepared and d) treated PVA films with doped (R)-1 (w (R)-1 :w PVA = 1 : 600) at room temperature with 290 nm excitation. (inset: photographs of films under 254 nm excitation on and off).

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“…Chem. Soc.20211431852718535 . This work describes a promising and facile approach to achieving organic circularly polarized RTP copolymers through radical binary copolymerization, with a maximum phosphorescence quantum yield of 30.6% and the largest dissymmetric factor of 9.4 × 10 –3 .…”

Section: Key Referencesmentioning

confidence: 99%

Long-Lived Organic Room-Temperature Phosphorescence from Amorphous Polymer Systems

2022

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS: Long-lived organic room-temperature phosphorescence (RTP) materials have recently drawn extensive attention because of their promising applications in information security, biological imaging, optoelectronic devices, and intelligent sensors.In contrast to conventional fluorescence, the RTP phenomenon originates from the slow radiative transition of triplet excitons. Thus, enhancing the intersystem crossing (ISC) rate from the lowest excited singlet state (S 1 ) to the excited triplet state and suppressing the nonradiative relaxation channels of the lowest excited triplet state (T 1 ) are reasonable methods for realizing highly efficient RTP in purely organic materials. Over the past few decades, many strategies have been designed on the basis of the above two crucial factors. The introduction of heavy atoms, aromatic carbonyl groups, and other heteroatoms with abundant lone-pair electrons has been demonstrated to strengthen the spin− orbit coupling, thereby successfully facilitating the ISC process. Furthermore, the rigid environment is commonly constructed through crystal engineering to restrict intramolecular motions and intermolecular collisions to decrease excited-state energy dissipation. However, most crystal-based organic RTP materials suffer from poor processability, flexibility, and reproducibility, becoming a thorny obstacle to their practical application. Amorphous organic polymers with long-lived RTP characteristics are more competitive in materials science. The intertwined structures and long chains of polymers not only ensure the rigid environment with multiple interactions but also protect triplet excitons from the surroundings, which are conducive to realizing ultralong and bright RTP emission. Exploring the fabrication strategies, intrinsic mechanisms, and practical applications of organic long-lived RTP polymers is highly desirable but remains a formidable challenge. In particular, intelligent organic RTP polymer systems that are capable of dynamically responding to external stimuli (e.g., light, temperature, oxygen, and humidity) have been rarely reported. To develop multifunctional RTP materials and expand their potential applications, a great amount of effort has been expended. This Account gives a summary of the significant advances in amorphous organic RTP polymer systems, especially smart stimulusresponsive ones, focusing on the construction of a rigid environment to suppress nonradiative deactivation by abundant inter/ intramolecular interactions. The typical interactions in RTP polymer systems mainly include hydrogen bonding, ionic bonding, and covalent bonding, which can change the molecular electronic structures and affect the energy dissipation channels of the excited states. An in-depth understanding of intrinsic mechanisms and an extensive exploration of potential applications for excitationdependent color-tunable, ultraviolet (UV) irradiation-activated, temperature-dependent, water-responsive, and circula...

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Circularly Polarized Organic Room Temperature Phosphorescence from Amorphous Copolymers

Cited by 151 publications

References 45 publications

Ultraviolet Light Detectable Circularly Polarized Room Temperature Phosphorescence in Chiral Naphthalimide Self-Assemblies

Ultraviolet Light Detectable Circularly Polarized Room Temperature Phosphorescence in Chiral Naphthalimide Self-Assemblies

Strong Circularly‐Polarized Room‐Temperature Phosphorescence from a Feasibly Separable Scaffold of Bidibenzo[b,d]furan with Locked Axial Chirality

Long-Lived Organic Room-Temperature Phosphorescence from Amorphous Polymer Systems

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