手性有机小分子圆偏振发光的研究进展

圆偏振发光不仅能直观地反映手性发光体系的激发态结构信息,而且在3D显示、自旋信息通讯、信息存储与处理、CPL激光、生物探针等领域具有广泛的应用前景.因此,近年来圆偏振发光材料引起了人们越来越多的兴趣与关注,成为有机发光功能材料领域一个新的研究热点.本综述总结近年来关于手性有机小分子圆偏振发光的研究进展,主要围绕具有中心手性、轴手性、面手性和螺旋手性的圆偏振发光有机小分子展开介绍.     

Circularly Polarized Luminescence in Supramolecular Assemblies of Chiral Bichromophoric Perylene Bisimides

Chiral bichromophoric perylene bisimides are demonstrated as active materials of circularly polarized emission. The bichromophoric system exhibited circularly polarized luminescence with dissymmetry factors typical of that of similar organic chiral chromophoric systems in the monomeric state. Variation in solvent composition led to the formation of stably soluble helical aggregates through intermolecular interactions. A large enhancement in the dissymmetry of circularly polarized luminescence was exhibited by the aggregated structures both in the solution and solid states. The sum of excitonic couplings between the individual chromophoric units in the self‐assembled state results in relatively large dissymmetry in the circularly polarized luminescence, thereby giving rise to enhanced dissymmetry factors for the aggregated structures. The spacer between chiral center and chromophoric units played a crucial role in the effective enhancement of chiroptical properties in the self‐assembled structures. These materials might provide opportunities for the design of a new class of functional bichromophoric organic nanoarchitectures that can find potential applications in the field of chiroptical memory and light‐emitting devices based on supramolecular electronics.     

Anomalous Lehmann Rotation of Achiral Nematic Liquid Crystal Droplets Trapped under Linearly Polarized Optical Tweezers

Continuous rotation of a cholesteric droplet under the heat gradient was observed by Lehmann in 1900. This phenomenon, the so-called Lehmann effect, consists of unidirectional rotation around the heat flux axis. We investigate this gradient heat effect using infrared laser optical tweezers. By applying single trap linearly polarized optical tweezers onto a radial achiral nematic liquid crystal droplet, trapping of the droplet was performed. However, under a linearly polarized optical trap, instead of stable trapping of the droplet with slightly deformed molecular directors along with a radial hedgehog defect, anomalous continuous rotation of the droplet was observed. Under low power laser trapping, the droplet appeared to rotate clockwise. By continuously increasing the laser power, a stable trap was observed, followed by reverse directional rotation in a higher intensity laser trap. Optical levitation of the droplet in the laser beam caused the heat gradient, and a breaking of the symmetry of the achiral nematic droplet. These two effects together led to the rotation of the droplet under linearly polarized laser trapping, with the sense of rotation depending on laser power.     

A Nanohelicoidal Nematic Liquid Crystal Formed by a Non‐Linear Duplexed Hexamer

The twist‐bend modulated nematic liquid‐crystal phase exhibits formation of a nanometre‐scale helical pitch in a fluid and spontaneous breaking of mirror symmetry, leading to a quasi‐fluid state composed of chiral domains despite being composed of achiral materials. This phase was only observed for materials with two or more mesogenic units, the manner of attachment between which is always linear. Non‐linear oligomers with a H‐shaped hexamesogen are now found to exhibit both nematic and twist‐bend modulated nematic phases. This shatters the assumption that a linear sequence of mesogenic units is a prerequisite for this phase, and points to this state of matter being exhibited by a wider range of self‐assembling structures than was previously envisaged. These results support the double helix model of the TB phase as opposed to the simple heliconical model. This new class of materials could act as low‐molecular‐weight surrogates for cross‐linked liquid‐crystalline elastomers.     

Sign Reversal of a Large Circularly Polarized Luminescence Signal by the Twisting Motion of a Bidentate Ligand

This work demonstrates sign reversal of large circularly polarized luminescence (CPL) signal based on the hinge‐like twisting motion of a bidentate ligand, 3,3‐bis(diphenylphosphoryl)‐2,2‐bipyridine (BIPYPO), in a cis–trans isomerization of chiral europium(III) complexes. X‐ray diffraction analysis revealed that twisting motion of BIPYPO provides s‐cis and s‐trans geometries of a chiral Eu^III complex containing either tris[3‐(trifluoromethylhydroxymethylene)‐(+)‐camphorate] (D ‐ 1 ) or tris[3‐(heptafluoropropylhydroxymethylene)‐(+)‐camphorate] (D ‐ 2 ). The s‐cis Eu^III complexes show eight‐coordinate geometry around the Eu^III ion, in which the chelate between the phosphoryl oxygen and the Eu^III ion forces the s‐cis geometry of BIPYPO. In contrast, the phosphorus–nitrogen interaction provides a conformational lock for the s‐trans geometry of the BIPYPO ligand, inducing a quasi‐seven‐coordinate Eu^III complex. The difference in coordination geometry causes the sign change of the CPL signals between the s‐cis and s‐trans isomers, whereby the s‐cis and s‐trans isomers of Eu^III complexes exhibit the positive and negative CPL signals, respectively, for the ⁵D₀→⁷F₁ transition. The proportion of the s‐trans‐D ‐ 1 against s‐cis‐D ‐ 1 increases upon changing the solvent from [D₃]acetonitrile to [D₆]acetone, inducing a sign change of the CPL signals. The complexes D ‐ 1 and D ‐ 2 show a biexponential decay with two different lifetimes, suggesting two emitting species, that is, the s‐cis and s‐trans isomers of Eu^III complexes. In both cases, the proportions of the longer lifetime components (τ₁) decrease and instead the shorter lifetime components (τ₂) increase upon changing the solvent from [D₃]acetonitrile to [D₆]acetone.     

Strong and Reversible Circularly Polarized Luminescence Emission of a Chiral 1,8‐Naphthalimide Fluorophore Induced by Excimer Emission and Orderly Aggregation

Four chiral 1,2‐diaminocyclohexane (DACH)‐based molecules (R,R/S,S‐ 2 and R,R/S,S‐ 4 ) incorporating 1,8‐naphthalimide fluorophores exhibit strong circularly polarized luminescence (CPL) emission signals in common organic solvents. Interestingly, the reversed CPL signals can be observed in the aggregated state, which is due to the orderly aggregation.     

Near-Infrared Circularly Polarized Luminescence through Intramolecular Excimer Formation of Oligo(p-phenyleneethynylene)-Based Double Helicates

Carbon-based double helicates consisting of two anthracene-containing oligo(p-phenyleneethynylene) units and two flexible chiral 1,1′-binaphthyl units or two rigid chiral 9,9′-spirobifluorene units were developed. The curved oligo(p-phenyleneethynylene) fragments in the double helicates were successfully constructed by tin-mediated reductive aromatization. Helical oligo(p-phenyleneethynylene) double strands fixed by two rigid spirobifluorene units showed little structural change under photoirradiation, thereby emitting circularly polarized luminescence (CPL) in the visible region with a high quantum yield (Φ_PL=0.93). In contrast, flexible binaphthyl units induced dynamic structural change of the oligo(p-phenyleneethynylene) luminophores under photoirradiation, leading to strong CPL (|g_lum|=1.1×10⁻²) in the near-infrared (NIR) region. UV/Vis, circular dichroism (CD), CPL and NMR spectroscopic analyses of the binaphthyl-hinged double helicate suggested excimer formation between two π-conjugated strands in the excited state. Theoretical calculations highlight the importance of the tightly interlocked excimer structure of the carbon-based double helicate in controlling the angle between the electric and magnetic transition dipole moments for strong NIR CPL generation.     

Chiral Sensing of Various Amino Acids Using Induced Circularly Polarized Luminescence from Europium(III) Complexes of Phenanthroline Dicarboxylic Acid Derivatives

Circularly polarized luminescence (CPL) was observed from [Eu(dppda)₂]^? (dppda=4,7‐diphenyl‐1,10‐phenanthroline‐2,9‐dicarboxylic acid) and [Eu(pzpda)₂]^? (pzpda=pyrazino[2,3‐f][1,10]phenanthroline‐7,10‐dicarboxylic acid) in aqueous solutions containing various amino acids. The selectivity of these complexes towards amino acids enabled them to be used as chiral sensors and their behavior was compared with that of [Eu(pda)₂]^? (pda=1,10‐phenanthroline‐2,9‐dicarboxylic acid). As these Eu^III complexes have achiral D_2d structures under ordinary conditions, there were no CPL signals in the emission assigned to f–f transitions. However, when the solutions contained particular amino acids they exhibited detectable CPL signals with g_lum values of about 0.1 (g_lum=CPL/2 TL; TL=total luminescence). On examining 13 amino acids with these three Eu^III complexes, it was found that whether an amino acid induced a detectable CPL depended on the Eu^III complex ligands. For example, when ornithine was used as a chiral agent, only [Eu(dppda)₂]^? exhibited intense CPL in aqueous solutions of 10^?2 mol dm^?3. Steep amino acid concentration dependence suggested that CPL in [Eu(dppda)₂]^? and [Eu(pzpda)₂]^? was induced by the association of four or more amino acid molecules, whereas CPL in [Eu(pda)₂]^? was induced by association of two arginine molecules.     

Microscopic Imaging of Chiral Amino Acids in Agar Gel through Circularly Polarized Luminescence of EuIII Complex

We recently found that [Eu(pda)₂]^? (pda: 1,10‐phenanthroline‐2,9‐dicarboxylic acid), which has an achiral structure in crystals, exhibits circularly polarized luminescence (CPL) in aqueous solutions containing chiral amino acids such as arginine and histidine. CPL measurements were performed for agar gel, which includes an aqueous solution of [Eu(pda)₂]^? and chiral arginine or histidine. The spectral shape, concentration, and pH dependences on CPL intensity in the agar gels were very close to those in aqueous solutions, indicating that the CPL of the Eu^III complex in the agar gels was induced by mechanism similar to that in aqueous solutions. We performed spatially resolved CPL measurements using a laboratory‐built microscopic CPL spectroscopic system for agar‐gel samples, where d ‐ and l ‐ amino acids were separately dispersed. We successfully recorded CPL imaging maps showing spatial dispersions of d ‐ and l ‐amino acid in the agar gels.     

Induction of Strong and Tunable Circularly Polarized Luminescence of Nonchiral,Nonmetal, Low‐Molecular‐Weight Fluorophores Using Chiral Nanotemplates

A new strategy is described for generating strong circularly polarized luminescence with highly tunable emission bands through chiral induction in nonchiral, totally organic, low‐molecular‐weight fluorescent dyes by chiral nanotemplate systems. Our approach allows the first systematic investigation to clarify the correlation between the circular dichroism and circularly polarized luminescence intensities. As a result, a dilute solution system with the highest circularly polarized luminescence intensity achieved to date and a dissymmetry factor of over 0.1 was identified.     

Molecular Design,Circularly Polarized Luminescence,and Helical Self‐Assembly of Chiral Aggregation‐Induced Emission Molecules

Aggregation‐induced emission luminogens (AIEgens) are a new class of luminophors, which are non‐emissive in solution, but emit intensively upon aggregation. By properly designing the chemical structures of the AIEgens, their aggregation process can be tuned towards a desired direction to give diverse novel luminescent architectures of micelles, rods, and helical fibers. AIEgens represent a kind of promising building block for the fabrication of luminescent micro/nanostructures with controllable morphologies. In this review, we describe our recent work in this research area, focusing on the molecular design, circularly polarized luminescence properties, and helical self‐assembly behavior of AIEgens.     

Two‐Dimensional Skyrmion Lattice Formation in a Nematic Liquid Crystal Consisting of Highly Bent Banana Molecules

We synthesized a novel banana‐shaped molecule based on a 1,7‐naphthalene central core that exhibits a distinct mesomorphism of the nematic‐to‐nematic phase transition. Both the X‐ray profile and direct imaging of atomic force microscopy (AFM) investigations clearly indicates the formation of an anomalous nematic phase possessing a two‐dimensional (2D) tetragonal lattice with a large edge (ca. 59 Å) directed perpendicular to the director in the low‐temperature nematic phase. One plausible model is proposed by an analogy of skyrmion lattice in which two types of cylinders formed from left‐ and right‐handed twist‐bend helices stack into a 2D tetragonal lattice, diminishing the inversion domain wall.     

Influence of a Change in Helical Twisting Power of Photoresponsive Chiral Dopants on Rotational Manipulation of Micro‐Objects on the Surface of Chiral Nematic Liquid Crystalline Films

Herein we report a group of five planar chiral molecules as photon‐mode chiral switches for the reversible control of the self‐assembled superstructures of doped chiral nematic liquid crystals. The chiral switches are composed of an asymmetrically substituted aromatic moiety and a photoisomerizing azobenzene unit connected in a cyclic manner through methylene spacers of varying lengths. All the molecules show conformational restriction in the rotation of the asymmetrically substituted aromatic moiety in both the E and Z states of the azobenzene units resulting in planar chirality with separable enantiomers. Our newly synthesized compounds in pure enantiomeric form show high helical twisting power (HTP) in addition to an improved change in HTP between the E and Z states. The molecule with a diphenylnaphthalene unit shows the highest ever known initial helical twisting power among chiral dopants with planar chirality. In addition to the reversible tuning of reflection colors, we employed the enantiomers of these five compounds in combination with four nematic liquid crystalline hosts to study their properties as molecular machines; the change in HTP of the chiral dopant upon photoisomerization induces rotation of the texture of the liquid crystal surfaces. Importantly, this study has revealed a linear dependence of the ratio of the difference between HTPs before and after irradiation against the absolute value of the initial HTP, not the absolute value of the change in helical twisting power between two states, on the angle of rotation of micro‐objects on chiral nematic liquid crystalline films. This study has also revealed that a change in irradiation intensity does not affect the maximum angle of rotation, but it does affect the speed of rotational reorganization of the cholesteric helix.     

纳米晶纤维素手性向列型液晶相结构的形成、调控及应用

手性材料作为一种新型功能材料,尤其是其特殊的光学性能以及在传感器、对映体分离领域的潜在应用,已经引起众多科学研究者的广泛关注。纳米晶纤维素(NCC)基手性材料以其丰富的来源、简单的合成工艺、独特的光学性质以及良好的稳定性等成为当前手性材料研究的热点。本文综述了NCC及其手性向列型液晶相的形成机制,重点介绍了NCC手性结构的调控方法,包括NCC性质、环境条件以及添加剂对其手性结构的影响。最后,总结了近几年NCC手性结构在光电材料和模板剂方面的应用研究进展。     

AIE Triggers the Circularly Polarized Luminescence of Atomically Precise Enantiomeric Copper(I) Alkynyl Clusters

Atomically precise enantiomeric metal clusters are scarce, and copper(I) alkynyl clusters with intense circularly polarized luminescence (CPL) responses have not been reported. A pair of chiral alkynyl ligands, (R/S)‐2‐diphenyl‐2‐hydroxylmethylpyrrolidine‐1‐propyne (abbreviated as R/S‐DPM ) we successfully prepared and single crystals were characterized of optically pure enantiomeric pair of atomically‐precise copper(I) clusters, [Cu₁₄(R/S‐DPM)₈](PF₆)₆ (denoted as R/S‐Cu₁₄ ), which feature bright red luminescence and CPL with a high luminescence anisotropy factor (g_lum). A dilute solution containing R/S‐Cu₁₄ was nonluminescent and CPL inactive at room temperature. Crystallization‐ and aggregation‐induced emission (CIE and AIE, respectively) contribute to the triggering of the CPL of R/S‐Cu₁₄ in the crystalline and aggregated states. Their AIE behavior and good biocompatibility indicated applications of these copper(I) clusters in cell imaging in HeLa and NG108‐15 cells.     

Planar Chiral Organoboranes with Thermoresponsive Emission and Circularly Polarized Luminescence: Integration of Pillar[5]arenes with Boron Chemistry

Enantiopure molecules based on macrocyclic architecture are unique for applications in enantioselective host‐guest recognition, chiral sensing and asymmetric catalysis. Taking advantage of the chiral transfer from the intrinsically planar chirality of pillar[5]arenes, we herein present an efficient and straightforward approach to achieve early examples of highly luminescent chiral systems ( P5NN and P5BN ). The optical resolution of their enantiomers has been carried out via preparative chiral HPLC, which was ascribed to the molecular functionalization of pillar[5]arenes with π‐conjugated, sterically bulky triarylamine (Ar₃N) as an electron donor and triarylborane (Ar₃B) as an acceptor. This crucial design enabled investigations of the chiroptical properties, including circular dichroism (CD) and circularly polarized luminescence (CPL) in the solid state. The intramolecular charge transfer (ICT) nature in P5BN afforded an interesting thermochromic shift of the emission over a wide temperature range.     

Circularly Polarized Luminescence of Chiral Perylene Diimide Based Enantiomers Triggered by Supramolecular Self‐Assembly

Two perylene diimide (PDI) enantiomers ( d/l ‐PDI ) incorporating the d /l ‐alanine moiety have been designed and synthesized. d/l ‐PDI in chloroform displays bright‐yellow fluorescence that is redshifted to orange‐red when the solvent contains a methanol fraction of 99 vol %. No circular dichroism (CD) or circularly polarized luminescence (CPL) signals were observed for d/l ‐PDI enantiomers in CHCl₃. Interestingly, the d/l ‐PDI enantiomers exhibit clear mirror‐image Cotton effects and CPL emission in the aggregate state. The optical anisotropy factor (g_lum) is as high as 0.02 at f_m=99 %, which can be attributed to self‐assembly through intermolecular π–π interactions in the aggregate state.     

Cover Feature: Chirality Transfer from an Innately Chiral Nanocrystal Core to a Nematic Liquid Crystal 2: Lyotropic Chromonic Liquid Crystals (ChemPhysChem 3/2023)

The importance of and the difference between molecular versus structural core chirality of substances that form nanomaterials, and their ability to transmit and amplify their chirality to and within a surrounding condensed medium is yet to be exactly understood. Here we demonstrate that neat as well as disodium cromoglycate (DSCG) surface-modified cellulose nanocrystals (CNCs) with both molecular and morphological core chirality can induce homochirality in racemic nematic lyotropic chromonic liquid crystal (rac-N-LCLC) tactoids. In comparison to the parent chiral organic building blocks, D-glucose, endowed only with molecular chirality, both CNCs showed a superior chirality transfer ability. Here, particularly the structurally compatible DSCG-modified CNCs prove to be highly effective since the surface DSCG moieties can insert into the DSCG stacks that constitute the racemic tactoids. Overall, this presents a highly efficient pathway for chiral induction in an aqueous medium and thus for understanding the origins of biological homochirality in a suitable experimental system.