Achiral Acceptor Research Articles

Integration of Wallach's Rule into Intermolecular Charge Transfer: A Visual Strategy for Chiral Purification.

Exploring the molecular packing and interaction between chiral molecules, no matter single enantiomer or racemates, is important for recognition and resolution of chiral drugs. However, sensitive and non-destructive analysis methods are lacking. Herein, an intermolecular-charge transfer (ICT) based spectroscopy is reported to reveal the differences in interaction between the achiral acceptor 1,2,4,5-tetracyanobenzene (TCNB) and the chiral donors, including S, R, and racemic naproxen (S/R/rac-NAP). In this process, S-NAP+TCNB and R-NAP+TCNB display a narrower band gap attributed to the newly formed ICT state. In contrast, the mixed rac-NAP and TCNB exhibit almost no significant change due to the strong affinity between the stereoisomers according to the Wallach's rule. Thus, S/R-NAP can be easily distinguished from rac-NAP based on significantly different optical behavior. The single crystal analysis, infrared spectroscopy, fluorescence spectroscopy, and theoretical calculation of naproxen confirm the importance of carboxyl for this differentiation in molecular packing and interaction. In addition, the esterification derivatization of naproxen achieves the manipulation of the intermolecular interaction model of racemates from the absolute Wallach's rule to a coexisting form of Wallach's rule and ICT. Further, visualized chiral purification of naproxen by the simple cocrystallization method is achieved through the collaboration of ICT and Wallach's rule.

Stepwise Solution-Interfacial Nanoarchitectonics for Assembled Film with Full-Color and White-Light Circularly Polarized Luminescence.

The fabrication of chiral thin films with tunable circularly polarized luminescence (CPL) colors is important in developing chiroptical materials but remains challenging due to the lack of assembly-initiated chiral film formation methodology. Here, by adopting a combined solution aggregation and interfacial assembly strategy, we report the fabrication of chiral film materials with full-color and white-light CPL. A biquinoline glutamic acid ester (abbreviated as BQGE) shows a typical aggregation-induced emission property with blue CPL after solution aggregation. Subsequent interfacial assembly of these solution aggregates on a solid substrate leads to the formation of a CPL active film consisting of nanobelt structures. Since the BQGE molecule has a coordination site, the CPL emission of an individual BQGE film can be extended from blue to green emission upon coordination with a zinc ion, accompanied by morphology transition from nanobelts to nanofibers. Further extension to red-color CPL is successfully achieved by coassembly with an achiral acceptor dye. Interestingly, the proper combination of coordination ratio and acceptor loading ratio provides bright white-light CPL emission from the BQGE/Zn2+/PDA triad composite film. This work provides a new approach to fabricating chiroptical film materials with controlled microscopic morphology and tunable CPL properties.

Circularly Polarized Fluorescence Energy Transfer for Constructing Multicolor Circularly Polarized Luminescence Films with Controllable Handedness

Utilizing achiral fluorophores to fabricate circularly polarized luminescence (CPL) materials is of significant importance in both fundamental research and practical applications; chirality transfer has become an indispensable process in routine efforts reported so far. However, this may restrict or even become a bottleneck in further advancing CPL materials starting from achiral fluorophores. Inspired by biological light-harvesting architectural systems, we attempt to establish a new strategy, i.e., circularly polarized fluorescence energy transfer (CPF-ET) to explore multicolor CPL films in the absence of chirality transfer. CPL has been successfully realized through both radiative energy transfer and nonradiative energy transfer. The material systems consist of chiral fluorescent helical polyacetylene working as a circularly fluorescence polarized energy donor and achiral fluorophores as an energy acceptor. Achiral acceptors absorb circularly polarized fluorescence energy from the donor and hence emit the corresponding CPL; accordingly, chirality transfer is no longer an indispensable condition, and the sense of the CPL emission of the achiral fluorophores is controlled by the chiral fluorescent polymer. Moreover, multicolor CPL films can be simply prepared by employing varying achiral fluorophores. This work provides a facile and versatile platform for achieving CPL by taking advantage of achiral fluorophores.

Cascade energy transfer boosted near-infrared circularly polarized luminescence of nanofibers from an exclusively achiral system.

We constructed chiral supramolecular nanofibers for light harvesting based on symmetry-breaking, and these can generate near-infrared circularly polarized luminescence (CPL) with high dissymmetry factor (glum) through a synergistic energy transfer and chirality transfer process. Firstly, the achiral molecule BTABA was assembled into a symmetry-breaking assembly using a seeded vortex strategy. Subsequently, the chiral assembly can endow the two achiral acceptors, Nile Red (NR) and Cyanine 7 (CY7), with supramolecular chirality, as well as chiroptical properties. CY7 can reach an excited state and emit near-infrared light through a cascade energy transfer process from BTABA to NR and then to CY7, but cannot directly acquire energy from the excited BTABA. Significantly, the near-infrared CPL of CY7 can be obtained with a boosted glum value of 0.03. This work will provide a deep insight into the preparation of materials with near-infrared CPL activity from an exclusively achiral system.

Polarization-induced nanohelixes of organic cocrystals from asymmetric components with dopant-induced chirality inversion.

Supramolecular chirality is essential for the development of functional materials. In this study, we report the synthesis of twisted nanobelts based on charge-transfer (CT) complexes using self-assembly cocrystallization starting from asymmetric components. An asymmetric donor, DBCz, and a typical acceptor, tetracyanoquinodimethane, were used to construct a chiral crystal architecture. An asymmetric alignment of the donor molecules induced polar ±(102) facets that, accompanied with free-standing growth, resulted in a twisting along the b-axis due to the electrostatic repulsive interactions. Meanwhile, the alternately oriented ±(001) side-facets were responsible for the propensity of the helixes to be right-handed. Addition of a dopant significantly enhanced the twisting probability by reducing the surface tension and adhesion influence, even switching the chirality preference of the helixes. In addition, we could further extend the synthetic route to other CT systems for formation of other chiral micro/nanostructures. Our study offers a novel design approach for chiral organic micro/nanostructures for applications in optically active systems, micro/nano-mechanical systems and biosensing.

Tunable Multicolor Circularly Polarized Luminescence via Co-assembly of One Chiral Electron Acceptor with Various Donors

Tunable Multicolor Circularly Polarized Luminescence via Co-assembly of One Chiral Electron Acceptor with Various Donors

High-Performance Circularly Polarized Electroluminescence with Simultaneous Narrowband Emission, High Efficiency, and Large Dissymmetry Factor.

Organic light-emitting diodes (OLEDs) that can simultaneously achieve narrowband emission, high efficiency, and circularly polarized luminescence remain a formidable challenge. In this study, a simple strategy is developed to address this challenge. A chiral exciplex-forming co-host is first designed by employing a chiral donor and an achiral acceptor molecule. The chiral exciplex host enables an achiral green multiple-resonance thermally activated delayed fluorescence emitter to achieve high-performance circularly polarized electroluminescence (CP-EL) with a high external quantum efficiency of 33.2%, large electroluminescence dissymmetry factor of 2.8 × 10-3 , and a small full-width at half-maximum of 42nm. This work provides a general approach for realizing CP-EL using easily available achiral emitters and can significantly extend the scope of circularly polarized OLEDs.

Supramolecular Nanohelix Fabricated by Pillararene-Based Host–Guest System for Chirality Amplification, Transfer, and Circularly Polarized Luminescence in Water

Supramolecular Nanohelix Fabricated by Pillararene-Based Host–Guest System for Chirality Amplification, Transfer, and Circularly Polarized Luminescence in Water

Chiral binaphthylamine based emitters with donor-acceptor structures: Facile synthesis and circularly polarized luminescence

Materials capable of circularly polarized luminescence (CPL) have generated intensive interest for their potential applications. However, constructing chiral molecules with tunable CPL signals remains a challenge. In this paper, two pairs of binaphthylamine based chiral donors R/S-2 and R/S-3 were synthesized by Pd-catalyzed C–N coupling and intramolecular oxidative coupling with good yields. Then three pairs of chiral D-A type molecules R/S-4∼6 can be synthesized by introducing two kinds of achiral acceptors. The extention of the chiral binaphthy skeleton endows these chiral compounds with CPL signals ranged from 417 nm to 544 nm in solutions and film states. The glum can be up to −2.9 × 10−3 for R-2 in solution. The introduction of terephthalonitrile as acceptor endow R/S-4 thermally activated delayed fluorescence (TADF). Furthermore, when benzophenone is chosen as achiral acceptor, the obtained chiral D-A molecules R/S-5 and R/S-6 can exhibit reversed CPL signals compared with their corresponding chiral donors. This work demonstrates the introduction of chiral D-A structure not only alters the wavelength of the CPL signals but also can reverse the CPL sign.

Highly Selective High‐Speed Circularly Polarized Photodiodes Based on π‐Conjugated Polymers

AbstractChiral π‐conjugated molecular systems that are intrinsically sensitive to the handedness of circularly polarized (CP) light potentially allow for miniaturized, low‐cost CP detection devices. Such devices promise to transform several technologies, including biosensing, quantum optics, and communication of data encrypted by exploiting the spin angular momentum of light. Here a simple, bilayer organic photodiode (CP OPD) comprising an achiral π‐conjugated polymer–chiral additive blend as the electron donor layer and an achiral C60 electron acceptor layer is realized. These devices exhibit considerable photocurrent dissymmetry gph, with absolute values as high as 0.85 and dark currents as low as 10 pA. Impressively, they showcase a linear dynamic range of 80 dB, and rise and fall times of ≈7 µs, which significantly outperforms all previously reported CP selective photodetectors. Mechanistically, it is shown that the gph is sensitive to the thickness of both the chiral donor and achiral acceptor layers and that a trade‐off exists between the external quantum efficiency and gph. The fast‐switching speeds of these devices, coupled with their large dynamic range and highly selective response to CP light, opens up the possibility of their direct application in CP sensing and optical communications.

Luminescent Chiral Exciplexes with Sky-Blue and Green Circularly Polarized-Thermally Activated Delayed Fluorescence.

Luminescent exciplexes based on a chiral electron donor and achiral acceptors are reported as a new approach to design circularly polarized (CP) and thermally activated delayed fluorescence (TADF) emitters. This strategy results in rather high CP luminescence (CPL) values with glum up to 7×10-3 , one order of magnitude higher in comparison to the CPL signal recorded for the chiral donor alone (glum ∼7×10-4 ). This increase occurs concomitantly with a CPL sign inversion, as a result of the strong charge-transfer emission character, as experimentally and theoretically rationalized by using a covalent chiral donor-acceptor model. Interestingly, blue, green-yellow and red chiral luminescent exciplexes can be obtained by modifying with the electron accepting character of the achiral unit while keeping the same chiral donor unit. These results bring new (inter)molecular guidelines to obtain simply and efficiently multi-color CP-TADF emitters.

Circularly Polarized Fluorescence Resonance Energy Transfer (C‐FRET) for Efficient Chirality Transmission within an Intermolecular System

AbstractThe occurrence and transmission of chirality is a fascinating characteristic of nature. However, the intermolecular transmission efficiency of circularly polarized luminescence (CPL) remains challenging due to poor through‐space energy transfer. We report a unique CPL transmission from inducing the achiral acceptor to emit CPL within a specific liquid crystal (LC)‐based intermolecular system through a circularly polarized fluorescence resonance energy transfer (C‐FRET), wherein the luminescent cholesteric LC is employed as the chirality donor, and rationally designed achiral long‐wavelength aggregation‐induced emission (AIE) fluorophore acts as the well‐assembled acceptor. In contrast to photon‐release‐and‐absorption, the chirality transmission channel ofC‐FRET is highly dependent upon the energy resonance in the highly intrinsic chiral assembly of cholesteric LC, as verified by deliberately separating the achiral acceptor from the chiral donor to keep it far beyond the resonance distance. ThisC‐FRET mode provides a de novo strategy concept for high‐level information processing for applications such as high‐density data storage, combinatorial logic calculation, and multilevel data encryption and decryption.

Circularly Polarized Fluorescence Resonance Energy Transfer (C-FRET) for Efficient Chirality Transmission within an Intermolecular System.

The occurrence and transmission of chirality is a fascinating characteristic of nature. However, the intermolecular transmission efficiency of circularly polarized luminescence (CPL) remains challenging due to poor through-space energy transfer. We report a unique CPL transmission from inducing the achiral acceptor to emit CPL within a specific liquid crystal (LC)-based intermolecular system through a circularly polarized fluorescence resonance energy transfer (C-FRET), wherein the luminescent cholesteric LC is employed as the chirality donor, and rationally designed achiral long-wavelength aggregation-induced emission (AIE) fluorophore acts as the well-assembled acceptor. In contrast to photon-release-and-absorption, the chirality transmission channel of C-FRET is highly dependent upon the energy resonance in the highly intrinsic chiral assembly of cholesteric LC, as verified by deliberately separating the achiral acceptor from the chiral donor to keep it far beyond the resonance distance. This C-FRET mode provides a de novo strategy concept for high-level information processing for applications such as high-density data storage, combinatorial logic calculation, and multilevel data encryption and decryption.

Guest-Induced Enantioselective Self-Assembly of a Pd6 Homochiral Octahedral Cage with a C3-Symmetric Pyridyl Donor.

Self-assembly of an achiral acceptor of square-planar Pd(II) or Pt(II) ion with a symmetric donor generally yields achiral architecture or a racemic mixture of chiral assemblies. Selective formation of an enantiopure assembly in such processes is very challenging. We report here a new approach of converting a dynamic mixture of multiple homochiral assemblies to an enantiopure architecture through the interaction of a chiral guest molecule. One-pot reaction of a cationic C3-symmetric tripyridyl donor L·HNO3 with cis-[(tmeda)Pd(NO3)2] (M) [tmeda = N,N,N',N'-tetramethylethane-1,2-diamine] yielded a complex mixture of stereoisomers of a chiral octahedral cage. Surprisingly, the presence of R-BINOL as a chiral guest in the above self-assembly induced selective formation of a single enantiopure octahedral cage. S-BINOL induced formation of the other enantiomer of the cage selectively. While selective recognition of an enantiomeric guest from a racemic mixture by a chiral host is well-known, present observation of "reverse chiral recognition" where the guest molecule determines the handedness of the host leading to the formation of an enantiopure cage is noteworthy.

Enhanced Circularly Polarized Luminescence in Emissive Charge-Transfer Complexes.

Achieving a large dissymmetry factor (glum ) is a challenge in the field of circularly polarized luminescence (CPL). A chiral charge-transfer (CT) system consisting of chiral electron donor and achiral electron acceptor shows bright circularly polarized emission with large glum value. The chiral emissive CT complexes could be fabricated through various approaches, such as grinding, crystallization, spin coating, and gelatinization, by simply blending chiral donor and achiral acceptor. The structural synergy originating from π-π stacking and strong CT interactions resulted in the long-range ordered self-assembly, enabling the formation of supramolecular gels. Benefiting from the large magnetic dipole transition moment in the CT state, the CPL activity of CT complexes exhibited large circular polarization. Our design strategy of the chiral emissive CT complexes is expected to help the development of new molecular engineering strategies for designing highly efficient CPL-active materials.

Enhanced Circularly Polarized Luminescence in Emissive Charge‐Transfer Complexes

AbstractAchieving a large dissymmetry factor (glum) is a challenge in the field of circularly polarized luminescence (CPL). A chiral charge‐transfer (CT) system consisting of chiral electron donor and achiral electron acceptor shows bright circularly polarized emission with large glum value. The chiral emissive CT complexes could be fabricated through various approaches, such as grinding, crystallization, spin coating, and gelatinization, by simply blending chiral donor and achiral acceptor. The structural synergy originating from π–π stacking and strong CT interactions resulted in the long‐range ordered self‐assembly, enabling the formation of supramolecular gels. Benefiting from the large magnetic dipole transition moment in the CT state, the CPL activity of CT complexes exhibited large circular polarization. Our design strategy of the chiral emissive CT complexes is expected to help the development of new molecular engineering strategies for designing highly efficient CPL‐active materials.

Cooperative Chirality and Sequential Energy Transfer in a Supramolecular Light-Harvesting Nanotube.

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.

Cooperative Chirality and Sequential Energy Transfer in a Supramolecular Light‐Harvesting Nanotube

AbstractBy 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.

Chirality and energy transfer amplified circularly polarized luminescence in composite nanohelix

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).

Excited‐State Proton Transfer in Chiral Environments: Photoracemization of BINOLs

We have studied excited-state proton transfer (ESPT) from chiral proton donors to chiral and achiral acceptors. The key role of the exergonicity of the reaction and the transition-state position along the reaction coordinate for the existence of an enantiomeric effect was established. This effect was observed for "super" photoacids (ΔG ≪ 0) and vanished for endergonic reactions (ΔG > 0) where a "late" transition state similar to planar achiral binaphtholate anion occurs. As a result, photoracemization was observed, as confirmed by circular dichroism spectroscopy. The photoracemization effects were studied for several chiral photoacids (BINOLs and their ethers) and proton acceptors (amines, aminoalcohols, and water) using UV-vis, steady-state fluorescence, and time-resolved fluorescence spectroscopies. The nature of the solvent and the proton acceptor, as well as the chemical structure of the BINOL, played a pivotal role in the photochemical reactivity of the system. Two proposed pathways competed for photoracemization: excited-state inter- and intra-molecular proton transfer, the former being more effective. Irradiation of the dimethoxy BINOL derivative, which lacks an acidic proton and cannot undergo ESPT, produced no appreciable reaction or racemization.