An official website of the United States government
Metal‐halide perovskites are known for their strong and tunable luminescence. However, the synthesis of perovskite‐based particles with circularly polarized light emission (CPLE) remains challenging due to the complex interplay of metal‐ligand chemistries, crystallization patterns, and chirality transfer mechanisms. Achiral perovskites can be deposited on chiral “hedgehog” particles (CHIPs) with twisted spikes, producing chiroptically active materials with spectroscopic bands specific to the perovskite and chirality specific to the template CHIPs. Left‐ and right‐handed CPLE is engineered into complex particles comprised of a layer of perovskite deposited onto CHIPs coated with an intermediate silica layer. The spectral position of chiroptical bands, the optical asymmetryg‐factors, and single‐particle circularly polarized microscopy indicate that the observed CPLE is dominated by the post‐emission scattering from the twisted spikes of the parent particle. Templating luminescent nanofilms on CHIPs provides a simple pathway to a wide range of complex chiroptical materials; the dispersibility of the CHIPs in various solvents and the tunability of their chiral geometry enable their applications as single‐particle emitters with strong and controllable polarization rotation.
more »
« less
Transferred Chiroptical Transitions in Chiral Binaphthyl /π‐Conjugated Polymer Hybrid Films: Significance of Aromatic Solvent‐Mediated Co‐Crystallization
For advancing next‐generation optoelectronics, a versatile strategy for fabricating π‐conjugated polymer (π‐CP)/chiral‐small molecule (SM) hybrid films through co‐crystallization‐mediated chirality transfer is reported. The transfer of optical chirality from 1,1′‐binaphthyl–2,2′‐diamine (BN), a representative chiral inducer SM, to thin films of various achiral π‐CPs, including non‐fluorene π‐CPs, is achieved by simply blending the π‐CPs with BN using aromatic organic solvents. The resulting π‐CP/chiral‐SM hybrid films exhibit chiroptical responses at the main electronic absorption bands of various π‐CPs. Studies of the morphology, crystalline structure, and phase‐separation structure of a representative hybrid system of poly(3‐hexylthiophene) (P3HT) and BN reveal that these hybrid films exhibit a characteristic lamellar structure where the π‐CPs co‐crystallize with chiral BN molecules, facilitated by aromatic solvent‐assisted intermolecular π–π interactions. In‐depth photophysical analysis suggests that BN molecules co‐crystallized in the P3HT lamellar structure induce asymmetrically misaligned transition dipoles along the P3HT conjugated backbone, transferring optical chirality from BN to P3HT under circularly polarized light illumination. As a proof‐of‐concept, chiroptical photodiodes based on π‐CP/chiral‐SM hybrid films and printed micropatterns, exhibiting a distinguishable photocurrent response depending on the direction of circularly polarized light are successfully demonstrated.
more »
« less
- Award ID(s):
- 2154617
- PAR ID:
- 10546613
- Publisher / Repository:
- Wiley-VCH GmbH
- Date Published:
- Journal Name:
- Advanced Functional Materials
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
π-Helical push–pull dyes were prepared and their (chir)optical properties were investigated both experimentally and computationally. Specific fluorescent behaviour of bis-substituted system was observed with unprecedented solvent effect on the intensity of circularly polarized luminescence (CPL, dissymmetry factor decreasing from 10 −2 to 10 −3 with an increase in solvent polarity) that was linked to a change in symmetry of chiral excited state and suppression of interbranched exciton coupling. The results highlight the potential of CPL spectroscopy to study and provide a deeper understanding of electronic photophysical processes in chiral π-conjugated molecules.more » « less
-
Abstract Natural polymers, particularly plant‐derived nanocelluloses, self‐organize into hierarchical structures, enabling mechanical robustness, bright iridescence, emission, and polarized light reflection. These biophotonic properties are facilitated by the assembly of individual components during evaporation, such as cellulose nanocrystals (CNCs), which exhibit a left‐handed helical pitch in a chiral nematic state. This work demonstrates how optically active films with pre‐programmed opposite handedness (left or right) can be constructed via shear‐induced twisted printing with clockwise and counter‐clockwise shearing vectors. The resulting large‐area thin films are transparent yet exhibit pre‐determined mirror‐symmetrical optical activity, enabling the distinction of absorbed and emitted circularly polarized light. This processing method allows for sequential printing of thin and ultrathin films with twisted layered organization and on‐demand helicity. The complex light polarization behavior is due to step‐like changes in linear birefringence within each deposited layer and circular birefringence, different from that of conventional CNC films as revealed with Muller matrix analysis. Furthermore, intercalating an achiral organic dye into printed structures induces circularly polarized luminescence while preserving high transmittance and controlled handedness. These results suggest that twisted sequential printing can facilitate the construction of chiroptical metamaterials with tunable circular polarization, absorption, and emission for optical filters, encryption, photonic coatings, and chiral sensors.more » « less
-
Abstract Magnetic fields are uniquely valuable for creating colloidal nanostructured materials, not only providing a means for controlled synthesis but also guiding their self‐assembly into distinct superstructures. In this study, a magnetothermal process for synthesizing hybrid nanostructures comprising ferrimagnetic magnetite nanorods coated with fluorescent perovskite nanocrystals is reported and their magnetic assembly into superstructures capable of emitting linear and circularly polarized light are demonstrated. Under UV excitation, the superstructures assembled in a liner magnetic field produce linear polarized luminescence, and those assembled in a chiral magnetic field exhibit strong circularly polarized luminescence (CPL) with aglumvalue up to 0.44 (±0.004). The CPL is believed to originate from the dipolar interaction between neighboring perovskite nanocrystals attached to the chiral assemblies and the chiral‐selective absorption of the perovskite emission by the magnetite phase. The magnetic synthesis and assembly approaches and the resulting distinctive chiral superstructures are anticipated to open up new avenues for designing diverse functional chiroptical devices.more » « less
-
null (Ed.)While the development of chiral molecules displaying circularly polarized luminescence (CPL) has received considerable attention, the corresponding CPL intensity, g lum, hardly exceeds 10 −2 at the molecular level owing to the difficulty in optimizing the key parameters governing such a luminescence process. To address this challenge, we report here the synthesis and chiroptical properties of a new family of π-helical push–pull systems based on carbo[6]helicene, where the latter acts as either a chiral electron acceptor or a donor unit. This comprehensive experimental and theoretical investigation shows that the magnitude and relative orientation of the electric ( μe ) and magnetic (μ m ) dipole transition moments can be tuned efficiently with regard to the molecular chiroptical properties, which results in high g lum values, i.e. up to 3–4 × 10 −2 . Our investigations revealed that the optimized mutual orientation of the electric and magnetic dipoles in the excited state is a crucial parameter to achieve intense helicene-mediated exciton coupling, which is a major contributor to the obtained strong CPL. Finally, top-emission CP-OLEDs were fabricated through vapor deposition, which afforded a promising g El of around 8 × 10 −3 . These results bring about further molecular design guidelines to reach high CPL intensity and offer new insights into the development of innovative CP-OLED architectures.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1002/adfm.202409982
