Yutao Sang obtained his B.Sc. and M.Sc. degrees in chemistry from Qingdao University, China. In 2016, he enrolled on a Ph.D. course at the Institute of Chemistry, Chinese Academy of Sciences (ICCAS), under the supervision of Prof. Minghua Liu, where he is currently in his third year. His ongoing research includes supramolecular chirality, chiroptical materials, and symmetry breaking of achiral molecules in gels and related systems. Pengfei Duan received his Ph.D. degree from the Institute of Chemistry, Chinese Academy of Sciences (CAS) in 2011 with Prof. Minghua Liu on chiral selfassembly in colloid and interface chemistry. He was a postdoctoral research fellow with Prof. Nobuo Kimizuka at Kyushu University, working on photon upconversion in self-assembled systems. In 2015, he became a professor at the National Center for Nanoscience and Technology (NCNST). His current research interests focus on photochemistry and photophysics in chiral supramolecular systems.
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).
Efficient triplet-triplet annihilation (TTA)-based photon upconversion (UC) is achieved in supramolecular organogel matrixes. Intense UC emission was observed from donor (sensitizer)-acceptor (emitter) pairs in organogels even under air-saturated condition, which solved a major problem: deactivation of excited triplet states and TTA-UC by molecular oxygen. These unique TTA-UC molecular systems were formed by spontaneous accumulation of donor and acceptor molecules in the gel nanofibers which are stabilized by developed hydrogen bond networks. These molecules preorganized in nanofibers showed efficient transfer and migration of triplet energy, as revealed by a series of spectroscopic, microscopic, and rheological characterizations. Surprisingly, the donor and acceptor molecules incorporated in nanofibers are significantly protected from the quenching action of dissolved molecular oxygen, indicating very low solubility of oxygen to nanofibers. In addition, efficient TTA-UC is achieved even under excitation power lower than the solar irradiance. These observations clearly unveil the adaptive feature of host gel nanofiber networks that allows efficient and cooperative inclusion of donor-acceptor molecules while maintaining their structural integrity. As evidence, thermally induced reversible assembly/disassembly of supramolecular gel networks lead to reversible modulation of the UC emission intensity. Moreover, the air-stable TTA-UC in supramolecular gel nanofibers was generally observed for a wide combination of donor-acceptor pairs which enabled near IR-to-yellow, red-to-cyan, green-to-blue, and blue-to-UV wavelength conversions. These findings provide a new perspective of air-stable TTA-UC molecular systems; spontaneous and adaptive accumulation of donor and acceptor molecules in oxygen-blocking, self-assembled nanomatrixes. The oxygen-barrier property of l-glutamate-derived organogel nanofibers has been unveiled for the first time, which could find many applications in stabilizing air-sensitive species in aerated systems.
Perovskite nanocrystals are attracting great interest due to their excellent photonic properties. Here, through a supramolecular self-assembly approach, the perovskite nanocrystals (NCs) with a novel circularly polarized luminescence (CPL) are successfully endowed. It is found that the achiral perovskite NCs can coassemble with chiral gelator in nonpolar solvents, in which the gelator molecules modify the surface of the perovskite NCs. Through such cogelation, the molecular chirality can transfer to the NCs resulting in CPL signals with a dissymmetric factor (g ) up to 10 . Furthermore, depending on the molecular chirality of the gelator, the CPL sense can be selected and the mirror-imaged CPL is obtained. Such gels can be further embedded into the polymer film to facilitate flexible CPL devices. It is envisaged that this approach will afford a new insight into the designing of the functional chiroptical 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.
A nonvolatile, in-air functioning liquid photon upconverting system is developed. A rationally designed triplet sensitizer (branched alkyl chain-modified Pt(II) porphyrin) is homogeneously doped in energy-harvesting liquid acceptors with a 9,10-diphenylanthracene unit. A significantly high upconversion quantum yield of ∼28% is achieved in the solvent-free liquid state, even under aerated conditions. The liquid upconversion system shows a sequence of efficient triplet energy transfer and migration of two itinerant excited states which eventually collide with each other to produce a singlet excited state of the acceptor. The observed insusceptibility of upconversion luminescence to oxygen indicates the sealing ability of molten alkyl chains introduced to liquefy chromophores. The involvement of the energy migration process in triplet-triplet annihilation (TTA) provides a new perspective in designing advanced photon upconversion systems.
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 C 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.
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