Currently, the development of circularly polarized luminescent (CPL) materials has drawn extensive attention due to the numerous potential applications in optical data storage, displays, backlights ...in 3D displays, and so on. While the fabrication of CPL‐active materials generally requires chiral luminescent molecules, the introduction of the “self‐assembly” concept offers a new perspective in obtaining the CPL‐active materials. Following this approach, various self‐assembled materials, including organic‐, inorganic‐, and hybrid systems can be endowed with CPL properties. Benefiting from the advantages of self‐assembly, not only chiral molecules, but also achiral species, as well as inorganic nanoparticles have potential to be self‐assembled into chiral nanoassemblies showing CPL activity. In addition, the dissymmetry factor, an important parameter of CPL materials, can be enhanced through various pathways of self‐assembly. Here, the present status and progress of self‐assembled nanomaterials with CPL activity are reviewed. An overview of the key factors in regulating chiral emission materials at the supramolecular level will largely boost their application in multidisciplinary fields.
Recent development of circularly polarized luminescent (CPL) materials has aroused extensive attention. The self‐assembly strategy is proposed to address the barriers of tedious syntheses and the restricted substitutes during the development of CPL‐active materials. By highlighting the meritorious findings, the present status and progress in this field are reviewed, with the aim of boosting the development of chiroptical materials.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Transfer of both chirality and energy information plays an important role in biological systems. Here we show a chiral donor π-gelator and assembled it with an achiral π-acceptor to see how chirality ...and energy can be transferred in a composite donor-acceptor system. It is found that the individual chiral gelator can self-assemble into nanohelix. In the presence of the achiral acceptor, the self-assembly can also proceed and lead to the formation of the composite nanohelix. In the composite nanohelix, an energy transfer is realized. Interestingly, in the composite nanohelix, the achiral acceptor can both capture the supramolecular chirality and collect the circularly polarized energy from the chiral donor, showing both supramolecular chirality and energy transfer amplified circularly polarized luminescence (ETACPL).
Circularly polarized luminescent materials with high dissymmetry factor (glum) have been attracting increasing attention due to their distinctive photonic properties. In this work, by incorporating ...upconversion nanoparticles (UCNPs) and CsPbBr3 perovskite nanocrystals (PKNCs) into a chiral nematic liquid crystal (N*LC), enhanced upconverted circularly polarized luminescence (UC‐CPL) based on a radiative energy transfer (RET) process from UCNPs to CsPbBr3 PKNCs is successfully implemented. By locating the emission peak of CsPbBr3 PKNCs at the center of the photonic bandgap of N*LC, the maximum glum value of UC‐CPL can be amplified to an extremely large value of 1.1. Meanwhile, upconverted emission of UCNPs can be significantly enhanced due to the band edge enhancement effect of the N*LC, subsequently enhancing the emission of the CsPbBr3 PKNCs through the RET process. In addition, an applied electric field can switch the upconverted emission of the UCNPs, as well as the RET process, enabling an electric‐field‐controlled UC‐CPL switch.
Upconverted circularly polarized luminescence (UC‐CPL) of CsPbBr3 perovskite nanocrystals based on a radiative energy‐transfer process from upconversion nanoparticles can be realized in chiral nematic liquid crystals. A very large dissymmetry factor of around 1.1 for the UC‐CPL is obtained. In addition, a voltage‐force‐regulated chiroptical switch of UC‐CPL is realized.
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Amplification of circularly polarized luminescence (CPL) is demonstrated in a triplet–triplet annihilation-based photon upconversion (TTA-UC) system. When chiral binaphthyldiamine acceptors are ...sensitized with an achiral Pt(II) octaethylporphine (PtOEP) in solution, upconverted circularly polarized luminescence (UC-CPL) were observed for the first time, in which the positive or negative circularly polarized emission could be obtained respectively, following the molecular chirality of the acceptors (R/S). More interestingly, one order of magnitude amplification of the dissymmetry factor g lum in UC-CPL was obtained in comparison with the normal promoted CPL. The multistep photophysical process of TTA-UC including triplet–triplet energy transfer (TTET) and triplet–triplet annihilation (TTA) have been suggested to enhance the UC-CPL, which provided a new strategy to design CPL materials with a higher dissymmetry factor.
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IJS, KILJ, NUK, PNG, UL, UM
Abstract
Chiral optical materials based on circularly polarized luminescence (CPL) have emerged rapidly due to their feasible applications in diverse fields of research. However, limited to the small ...luminescence dissymmetry factor (
g
lum
), real application examples have rarely been reported. Here, we present a complex system, which show intense circularly polarized ultraviolet luminescence (CPUVL) with large
g
lum
value, enabling a chiral UV light triggered enantioselective polymerization. By integrating sensitized triplet-triplet annihilation upconversion and CPL, both visible-to-UV upconversion emission and upconverted circularly polarized ultraviolet luminescence (UC-CPUVL) were obtained in the systems, built of chiral annihilator
R
(
S
)-4,12-biphenyl2,2paracyclophane (
R
-/
S
-TP), and a thermally activated delayed fluorescence (TADF) sensitizer. After dispersing this upconversion system into room-temperature nematic liquid crystal, induced chiral nematic liquid crystal could significantly amplify the
g
lum
value (0.19) of UC-CPUVL. Further, the UC-CPUVL emission has been used to trigger the enantioselective photopolymerization of diacetylene. This work paves the way for the further development of functional application of CPL active materials.
The design and fabrication of quantum dots (QDs) with circularly polarized luminescence (CPL) has been a great challenge in developing chiroptical materials. We herein propose an alternative to the ...use of chiral capping reagents on QDs for the fabrication of CPL‐active QDs that is based on the supramolecular self‐assembly of achiral QDs with chiral gelators. Full‐color‐tunable CPL‐active QDs were obtained by simple mixing or gelation of a chiral gelator and achiral 3‐mercaptopropionic acid capped QDs. In addition, the handedness of the CPL can be controlled by the supramolecular chirality of the gels. Moreover, QDs with circularly polarized white light emission were fabricated for the first time by tuning the blending ratio of colorful QDs in the gel. The chirality transfer in the co‐assembly of the achiral QDs with the gelator and the spacer effect of the capping reagents on the QD surface are also discussed. This work provides new insight into the design of functional chiroptical materials.
Circularly polarized luminescence (CPL) was observed for various co‐gels with nanotube structures that had been assembled from achiral quantum dots (QDs) and a chiral lipid gelator. Full‐color and white CPL was achieved through mixing several QDs with different colors with the chiral gelator.
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Circularly polarized luminescent (CPL) materials are currently attracting great interest. While a chiral building is usually necessary in order to obtain CPL materials, here, this study proposes a ...general approach for fabricating 1D circularly polarized luminescent nanoassemblies from achiral aromatic molecules or aggregation‐induced emissive compounds (AIEgens). It is found that a C3 symmetric chiral gelator can individually form hexagonal nanotube structures and encapsulate the guest molecules. When achiral AIEgens are encapsulated into the confined nanotubes via organogelation, the AIEgens will emit circularly polarized luminescence. Further, the direction of the CPL could be controlled by the supramolecular chirality of the nanotube. Remarkably, the approach is universal and various kinds of the AIEgens can be doped to show such property, providing a full‐color‐tunable circularly polarized luminescence.
Circularly polarized luminescence is observed from achiral dyes doped in confined chiral nanotube organogels which are assembled from C3 symmetric chiral gelators with hexagonal tubular structures. This provides a versatile approach for fabricating 1D circularly polarized luminescent materials.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
In this work, we demonstrate a room-temperature chiral liquid crystal which shows remarkable photon upconverted circularly polarized luminescence (UC-CPL). Circularly polarized luminescent materials ...with higher dissymmetry factor (
) underpin the basis for future applications. Since most chiral organic molecules have only a small
, it is vital to explore a new pathway to amplify the
of organic compounds. Here, by dispersing a chiral emitter and a triplet donor into a room-temperature nematic liquid crystal, highly efficient triplet-triplet annihilation-based photon upconversion (TTA-UC) and UC-CPL were observed in the induced chiral nematic liquid crystal (N*LC). Moreover, this system could simultaneously amplify the promoted circularly polarized luminescence (CPL) and the upconverted circularly polarized luminescence. The dissymmetry factors
of CPL and UC-CPL have been amplified by three orders of magnitude and one order of magnitude, respectively.
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Circularly polarized luminescent materials are of increasing attention due to their potential applications in advanced optical technologies, such as chiroptical devices and optical sensing. Recently, ...in all reported circularly polarized luminescent materials, high‐energy excitation results in low‐energy or downconverted circularly polarized luminescence (CPL) emission. Although photon upconversion—i.e., the conversion of low‐energy light into higher‐energy emission, with a wide variety of applications—has been widely reported, the integration of photon upconversion and CPL in one chiral system to achieve higher‐energy CPL emission has never been reported. Herein, a brief review is provided of recent achievements in photon‐upconverted CPL via the triplet–triplet annihilation mechanism, focusing on the amplified dissymmetry factor glum through energy transfer process and dual upconverted and downconverted CPL emission through chirality and energy transfer process.
Upconverted circularly polarized luminescence (UC‐CPL) via triplet–triplet annihilation‐based photon upconversion in chiral systems is an emerging topic in photochemistry and photophysics. The concept of this topic is described, and recent advances in the construction and application of UC‐CPL materials are highlighted. In addition, new functions emerging from UC‐CPL materials are presented.
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By constructing a supramolecular light‐harvesting chiral nanotube in the aqueous phase, we demonstrate a cooperative energy and chirality transfer. It was found that a cyanostilbene‐appended ...glutamate compound (CG) self‐assembled into helical nanotubes exhibiting both supramolecular chirality and circularly polarized luminescence (CPL). When two achiral acceptors, ThT and AO, with different energy bands were co‐assembled with the nanotube, the CG nanotube could transfer its chirality to both of the acceptors. The excitation energy could be transferred to ThT but only be sequentially transferred to AO. During this process, the CPL ascribed to the acceptor could be sequentially amplified. This work provides a new insight into the understanding the cooperative chirality and energy transfer in a chiral supramolecular system, which is similar to the natural light‐harvesting antennas.
On the other hand: When the achiral acceptors thioflavin T (ThT) and acridine orange (AO), with different energy bands, were co‐assembled with the nanotube CG it could transfer its chirality to both of the acceptors to give an enhancement of acceptor circularly polarized luminescence (CPL). The excitation energy could be transferred to ThT but only be sequentially transferred to AO.
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