Achieving persistent room-temperature phosphorescence (p-RTP), particularly those of tunable full-colors, from pure organic amorphous polymers is attractive but challenging. Particularly, those with tunable multicolor p-RTP in response to excitation wavelength and time are highly important but both fundamentally and technically underexplored. Here, a facile and general strategy toward color-tunable p-RTP from blue to orange-red based on amidation grafting of luminophores onto sodium alginate (SA) chains, resulting in amorphous polymers with distinct p-RTP and even impressively excitation-dependent and time-dependent afterglows is reported. p-RTP is associated with the unique semi-rigidified SA chains, effective hydrogen bonding network, and oxygen barrier properties of SA, whereas excitation-dependent and time-dependent afterglows should stem from the formation of diversified p-RTP emissive species with comparable but different lifetimes. These results outline a rational strategy toward amorphous smart luminophores with colorful, excitation-dependent, and time-dependent p-RTP, excellent solution processability, and film-forming ability for versatile applications.

Color‐Tunable, Excitation‐Dependent, and Time‐Dependent Afterglows from Pure Organic Amorphous Polymers

Nonconventional luminophores devoid of remarkable conjugates have attracted considerable attention due to their unique luminescence behaviors, updated luminescence mechanism of organics and promising applications in optoelectronic, biological and medical fields. Unlike classic luminogens consisting of molecular segments with greatly extended electron delocalization, these unorthodox luminophores generally possess nonconjugated structures based on subgroups such as ether (–O–), hydroxyl (–OH), halogens, carbonyl (CO), carboxyl (–COOH), cyano (CN), thioether (–S–), sulfoxide (SO), sulfone (OSO), phosphate, and aliphatic amine, as well as their grouped functionalities like amide, imide, anhydride and ureido. They can exhibit intriguing intrinsic luminescence, generally featuring concentration-enhanced emission, aggregation-induced emission, excitation-dependent luminescence and prevailing phosphorescence. Herein, we review the recent progress in exploring these nonconventional luminophores and discuss the current challenges and future perspectives. Notably, different mechanisms are reviewed and the clustering-triggered emission (CTE) mechanism is highlighted, which emphasizes the clustering of the above mentioned electron rich moieties and consequent electron delocalization along with conformation rigidification. The CTE mechanism seems widely applicable for diversified natural, synthetic and supramolecular systems.

Nonconventional luminophores: characteristics, advancements and perspectives.

An innovative transformation of organic luminescent materials in recent years has realised the exciting research area of ultralong room-temperature phosphorescence. Here the credit for the advancements goes to the rational design of new organic phosphors. The continuous effort in the area has yielded wide varieties of metal-free organic systems capable of extending the lifetime to several seconds under ambient conditions with high quantum yield and attractive afterglow properties. The various strategies adopted in the past decade to manipulate the fate of triplet excitons suggest a bright future for this class of materials. To analyze the underlying processes in detail, we have chosen high performing organic triplet emitters that utilized the best possible ways to achieve a lifetime above one second along with impressive quantum yield and afterglow properties. Such a case study describing different classes of metal-free organic phosphors and strategies adopted for the efficient management of triplet excitons will stimulate the development of better candidates for futuristic applications. This Perspective discusses the phosphorescence features of single- and multi-component crystalline assemblies, host–guest assemblies, polymers, and polymer-based systems under various classes of molecules. The various applications of the organic phosphors, along with future perspectives, are also highlighted.

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Efficient metal-free organic room temperature phosphors

Abstract Circularly polarized organic afterglow (CPOA) with both long-lived room-temperature phosphorescence (RTP) and circularly polarized luminescence (CPL) is currently attracting great interest, but the development of multicolor-tunable CPOA in a single-component material remains a formidable challenge. Here, we report an efficient strategy to achieve multicolor CPOA molecules through chiral clusterization by implanting chirality center into non-conjugated organic cluster. Owing to excitation-dependent emission of clusters, highly efficient and significantly tuned CPOA emissions from blue to yellowish-green with dissymmetry factor over 2.3 × 10 −3 and lifetime up to 587 ms are observed under different excitation wavelengths. With the distinguished color-tunable CPOA, the multicolor CPL displays and visual RTP detection of ultraviolent light wavelength are successfully constructed. These results not only provide a new paradigm for realization of multicolor-tunable CPOA materials in single-component molecular systems, but also offer new opportunities for expanding the applicability of CPL and RTP materials for diversified applications. 

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Single-component color-tunable circularly polarized organic afterglow through chiral clusterization

/pdf/single-component-color-tunable-circularly-polarized-organic-12cg4e16.pdf

Nonconventional luminophores without significant conjugations generally possess excitation-dependent photoluminescence (PL) owing to the coexistence of diverse clustered chromophores, which strongly implies the possibility of achieving color-tunable PL and/or persistent room temperature phosphorescence (p-RTP) from their crystals assisted by effective intermolecular interactions. Compared with traditional luminogens, however, nonconventional luminophores generally suffer from poor PL efficiencies. Here, inspired by the highly stable double-helix structure and multiple hydrogen bonds in DNA, we report a series of planar or twisted nonconventional luminophores based on hydantoin (HA), demonstrating unprecedentedly high PL/p-RTP efficiencies and p-RTP lifetimes of up to 87.5%/21.8% and 1.74 s, respectively, accompanying color-tunable p-RTP from sky-blue to yellowish-green. These findings will advance the exploitation of efficient nonconventional luminophores and provide deeper mechanistic insights into the origin of color-tunable p-RTP.

Nonconventional luminophores with unprecedented efficiencies and color-tunable afterglows

Summary Halogen···halogen (X···X) short contacts, especially halogen bonds (XBs), have been widely used in multifarious fields because of their bridging function among luminophores, as well as their well-known heavy atom effect. Little attention, however, has been paid to the luminescent ability of halogen clusters. It remains unknown whether they could be emissive. Herein, to our knowledge, we report the first examples of emissive halogen clusters with fluorescence-phosphorescence dual emission in an aggregated state and even under ambient conditions, which should be attributed to the extended delocalization through effective intra- and intermolecular X···X contacts. Additionally, multi-tunable luminescence in response to excitation wavelength, temperature, and compression is noticed. These results unveil the potential of halogen clusters as novel chromophores and may inspire further exploration of nonconventional luminophores involving halogen moieties.

Luminescent halogen clusters

Pure organic luminogens with long-persistent luminescence have been extensively studied, on account of their fundamental research significance and diverse utilizations in anticounterfeiting, bioimaging, encryption, organic light-emitting diodes, chemo-sensing, etc. However, time-dependent color-tunable afterglow is rarely reported, especially for single-component materials. In this work, we reported an organic luminogen with time-dependent afterglow, namely, benzoyleneurea (BEU), with multiple persistent room-temperature phosphorescence (p-RTP) and thermally activated delayed fluorescence (TADF) in single crystals. While the lifetime of TADF is relatively short (~1.2 ms), those for p-RTP are as long as around 369~754 ms. The comparable but different decay rates of diversified p-RTP emissions endow BEU crystals with obvious time-dependent afterglow. The existence of multiple emissions can be reasonably illustrated by the clustering-triggered emission (CTE) mechanism. Single-crystal structure illustrates that the combination of benzene ring and nonconventional chromophores of ureide helps facilitate divergent intermolecular interactions, which contribute to the formation of varying emissive species. Moreover, its methyl- and chloro-substituted derivatives show similar multiple p-RTP emissions. However, no time-dependent afterglows are observed in their crystals, due to the highly approaching lifetimes. The afterglow color variation of BEU crystals grants its applications in advanced anticounterfeiting field and information encryption.

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Time-Dependent Afterglow from a Single Component Organic Luminogen.

Persistent room-temperature phosphorescence (p-RTP) from pure organics is attractive due to its fundamental importance and potential applications in molecular imaging, sensing, encryption, anticounterfeiting, etc.1-4 Recently, efforts have been also made in obtaining color-tunable p-RTP in aromatic phosphors5 and nonconjugated polymers6,7. The origin of color-tunable p-RTP and the rational design of such luminogens, particularly those with explicit structure and molecular packing, remain challenging. Noteworthily, nonconventional luminophores without significant conjugations generally possess excitation-dependent photoluminescence (PL) because of the coexistence of diverse clustered chromophores6,8, which strongly implicates the possibility to achieve color-tunable p-RTP from their molecular crystals assisted by effective intermolecular interactions. Here, inspirited by the highly stable double-helix structure and multiple hydrogen bonds in DNA, we reported a series of nonconventional luminophores based on hydantoin (HA), which demonstrate excitation-dependent PL and color-tunable p-RTP from sky-blue to yellowish-green, accompanying unprecedentedly high PL and p-RTP efficiencies of up to 87.5% and 21.8%, respectively. Meanwhile, the p-RTP emissions are resistant to vigorous mechanical grinding, with lifetimes of up to 1.74 s. Such robust, color-tunable and highly efficient p-RTP render the luminophores promising for varying applications. These findings provide mechanism insights into the origin of color-tunable p-RTP, and surely advance the exploitation of efficient nonconventional luminophores.

/pdf/dna-inspirited-rational-construction-of-nonconventional-4w8d8wam6v.pdf

Saixing Tang

Papers

Nonconventional luminophores: characteristics, advancements and perspectives.

Nonconventional luminophores with unprecedented efficiencies and color-tunable afterglows

Luminescent halogen clusters

Time-Dependent Afterglow from a Single Component Organic Luminogen.

DNA Inspirited Rational Construction of Nonconventional Luminophores with Efficient and Color-Tunable Afterglow