Circularly Polarized Luminescence Properties Research Articles

Saucer[n]arenes: Synthesis, Structure, Complexation, and Guest-Induced Circularly Polarized Luminescence Property.

Macrocycles denoted as saucer[n]arenes (n=4,5) were easily synthesized by the one-pot condensation of 2,7-dimethoxynaphthalene (2,7-DMN) and paraformaldehyde in the presence of TFA or catalytic BF3 ⋅OEt2 . With 1,1-dimethylpiperidin-1-ium as the template, saucer[4]arene was selectively obtained. Crystal structures show that saucer[n]arenes are all composed of 2,7-DMN moiety bridged by the methylene groups at 1,6-positions: all of the 7-methoxy groups lie on one face, and all of the 2-methoxy groups lie on the other. Saucer[n]arenes exhibit strong fluorescence properties with the quantum yields of 19.6 % and 23.4 %. They form 1:1 complexes with ammonium salts in both solution and solid state (association constant up to 105 M-1 in CDCl3 ). Chiral quaternary ammonium salts can induce the chirality of the dynamically racemic inherently chiral saucer[n]arenes in solution, and thus show mirror-imaged circular dichroism signals and circularly polarized luminescence (CPL) properties.

Iodization-enhanced fluorescence and circularly polarized luminescence for dual-readout probe design

Circularly polarized luminescence (CPL) is a preferential emission from chiral systems. Introducing CPL to traditional small fluorescence probes will greatly enhance selectivity and sensitivity due to avoiding the background fluorescence. Small-molecule probes are practically useful for bioimaging and sensing but always suffer from weak CPL properties. To optimize chiral perturbation, the study of structure-CPL correlation is an urgent necessity. Here, we investigated the influence of 3, 3′-substituent of BINOL on optical properties and found that iodization could significantly enhance the fluorescence quantum yield (ΦF) and dissymmetry factor (|glum|). Based on this finding, we presented a strategy to design dual-readout probes emiting both robust total fluorescence and CPL upon activation. As an application example, we first designed a pair of thiols probes, R/S-P1, with the fluorescence readout showing good linear response to cysteine, and CPL signal displaying significant enhancement with |glum| from undetectable value to 0.7 × 10−3.

Chiral Thermally Activated Delayed Fluorescence Materials Based on R/S‐N2,N2′‐Diphenyl‐[1,1′‐binaphthalene]‐2,2′‐diamine Donor with Narrow Emission Spectra for Highly Efficient Circularly Polarized Electroluminescence

AbstractIn this study, two pairs of chiral thermally activated delayed fluorescence (TADF) materials enabling circularly polarized luminescence (CPL) named R/S‐p‐BAMCN (rod‐shape) and R/S‐o‐BAMCN (helix‐shape) are prepared based on a new pair of chiral donor (D*), R/S‐N2,N2′‐diphenyl‐[1,1′‐binaphthalene]‐2,2′‐diamine (R/S‐BAM), and two cyano (CN) acceptors. Due to the rigid molecular structure and special intramolecular arrangement, the chiral TADF materials show high photoluminescence quantum efficiency (up to 0.86) with narrow full‐width at half‐maximum (38 nm in cyclohexane, 51 nm in toluene) and photoluminescence dissymmetry factor (|gPL|) up to 5.3 × 10−3. Particularly, the circularly polarized OLEDs (CP‐OLEDs) with rod‐shaped R/S‐p‐BAMCN as the emitter show high device performances with the maximum external quantum efficiency nearing 28%. Meanwhile, the semi‐transparent CP‐OLEDs based on helix‐shaped R/S‐o‐BAMCN exhibit obvious circularly polarized electroluminescence (CPEL) properties with the electroluminescence |gEL| factors around 4.6 × 10−3. The strategy of rigid D*‐A‐D* structure with special arrangement of chiral donor provides a direct way to obtain efficient CP‐TADF materials with narrow emission spectra and promising CPL properties for better CPEL performance.

Preparation of twisted organic–inorganic hybrid silica bundles with circularly polarized luminescence by supramolecular templating polymerization

Circularly polarized luminescence (CPL) materials have attracted increasing attention because of their promising applications in optoelectronics and chiroptical sensing. However, silica-based organic–inorganic hybrid nanomaterials with CPL properties have been rarely reported. In this work, twisted hybrid silica bundles were prepared by supramolecular templating polymerization of tetraphenylethene-containing bis(triethoxysilane) and tetraethoxysilane using the self-assemblies of chiral low-molecular-weight gelators as templates. It was found that the chirality of the supramolecular templates was transferred to the hybrid silicas. The hybrid silicas emitted green CPL with the luminescence dissymmetry factor up to 1.2 × 10−3 and high fluorescence efficiency. This work presents a facile method to fabricate silica-based hybrid nanomaterials with CPL activity.

Planar Chiral [2.2]Paracyclophane-Based Thermally Activated Delayed Fluorescent Materials for Circularly Polarized Electroluminescence

This work describes the construction of a novel planar chiral [2.2]paracyclophane-based thermally activated delayed fluorescence (TADF)-active molecule with circularly polarized luminescence (CPL). The combination of the bulky planar chiral phenoxazinephane (PXZp) donor based [2.2]paracyclophane and triazine acceptor enables the highly efficient luminescence performances and excellent CPL properties. The enantiomers exhibit excellent TADF activities, the energy difference (ΔEST) between singlet and triplet of the molecule is only 0.03 eV. Notably, through solution-process, a yellow CP-OLEDs based on the molecule as the emitting layers displays high maximum brightness (Lmax) up to 34 293 cd m-2, maximum external quantum efficiency (EQEmax) up to 7.8% and remarkable CP-EL signal with gEL factor up to 4.6 × 10-3.

Porphyrin with circularly polarized luminescence in aggregated states

Porphyrin with circularly polarized luminescence (CPL) in aggregated state was seldom presented due to the strong aggregation-caused quenching (ACQ) effect at aggregation. This work designed and synthesized a novel porphyrin derivative (CPL-P) with good CPL behaviour in aggregated states based on the strong AIE-FRET effect and good chirality transfer of liquid crystalline porphyrin, which was constructed by using porphyrin unit as core with four AIE cyanostilbene groups bearing peripheral chiral alkyl chains. CPL-P exhibited orderly hexagonal columnar mesophase between 62.5 °C and 113.2 °C. It displayed excellent fluorescence emission at 640–760 nm in aggregated states due to the AIE-FRET effect between cyanostilbene unit and porphyrin moiety. Moreover, CPL-P showed the strong circular dichroism and CPL properties in aggregated states based on the effective chiral transfer of the spiral liquid crystalline self-assembly. The |glum| value for mesophase attained 6.6 × 10−3 based on the combining effect of AIE-FRET and chiral transfer. This research supplied a new strategy for transferring typical achiral porphyrin with ACQ effect to luminescent molecule with good CPL behaviour in aggregated state.

Chiral Helical Polymer/Perovskite Hybrid Nanofibers with Intense Circularly Polarized Luminescence.

Chiral perovskites with circularly polarized luminescence (CPL) performance have attracted tremendous attention. This contribution reports a convenient and universal strategy for constructing chiral helical polymer/perovskite hybrid nanofibers with outstanding CPL properties. The hybrid nanofibers are prepared through a one-step electrospinning method in which chiral helical polyacetylenes, perovskite nanocrystals, and polyacrylonitrile serve as a handed-selective fluorescence filter, fluorescent source, and electrospinning matrix, respectively. Specially, perovskite nanocrystals are in situ formed during the electrospinning process, which avoids the tedious process for preparing and purifying perovskites. The prepared hybrid nanofibers all exhibit good long-time stability in air, owing to the effective protection effect of polymer matrix. More importantly, intense CPL emissions with high dissymmetry factor up to 10-2 level are obtained in the hybrid nanofibers. Furthermore, the emission color of CPL can be easily tuned by adjusting the precursors of perovskites. This work provides an efficient technique toward various kinds of CPL-active perovskite nanomaterials for both scientific research and future practical applications.

Preparation of chiral luminescent liquid crystals and manipulation effect of phase structures on the circularly polarized luminescence property

A high efficiency circularly polarized chiral luminescent liquid crystal with tunable signal was constructed.

Development of Circularly Polarized Luminescence (CPL) Peptides Containing Pyrenylalanines and 2-Aminoisobutyric Acid

Chiral organic and organometallic luminophores that possess circularly polarized luminescence (CPL) properties in the near-ultraviolet to near-infrared region have several useful applications. However, the CPL properties are subject to inherent factors of the compounds; to date, studies on the CPL properties influenced by amino acids and peptides are scarce. Consequently, we developed peptide-pyrene organic luminophores exhibiting various CPL properties. It is conceivable that the peptide-pyrene organic luminophores can be obtained as aggregates when dissolved in a solution. It is also possible that the formation of aggregates makes it difficult to accurately examine the CPL of the peptide in the solution. This study showed that the introduction of sterically hindered 2-aminoisobutyric acid (Aib) units into the peptide backbone inhibits aggregate formation. The resulting luminophores exhibit CPL properties owing to the presence of pyrene units. The results of this study can form a basis for the design of future materials that use peptide-pyrene organic luminophores.

Maximizing Chiral Perturbation on Thermally Activated Delayed Fluorescence Emitters and Elaboration of the First Top-Emission Circularly Polarized OLED.

Molecular designs merging circularly polarized luminescence (CPL) and thermally activated delayed fluorescence (CP-TADF) using the concept of chiral perturbation appeared recently as a cornerstone for the development of efficient CP-organic light emitting diodes (CP-OLED). Such devices could strongly increase the energy efficiency and performances of conventional OLED displays, in which 50% of the emitted light is often lost due to the use of antiglare filters. In this context, herein, ten couples of enantiomers derived from novel chiral emitter designs are reported, exhibiting CPL, TADF, and aggregation induced enhancement emission properties (AIEE). Representing the first structure properties relationship investigation for CP-TADF materials, this thorough experimental and theoretical work highlights crucial findings on the key structural and electronic parameters (isomerism, nature of the carbazole substituents) governing the synergy between CPL and TADF properties. To conclude this study, the first top emission CP-OLED is elaborated as a new approach of generating CP light in comparison with classical bottom-emission CP-OLED architecture. Indeed, the top-emission configuration represents the only relevant device architecture for future microdisplay applications. Thereby, in addition to offer molecular guidelines to combine efficiently TADF and CPL properties, this study opens new avenues toward practical applications for CP-OLEDs.

New Perspectives to Trigger and Modulate Circularly Polarized Luminescence of Complex and Aggregated Systems: Energy Transfer, Photon Upconversion, Charge Transfer, and Organic Radical.

Chiral functional materials with circularly polarized luminescence (CPL) have risen rapidly in recent years because of their fascinating characteristics and potential applications in various research fields. CPL refers to the differential spontaneous emission of left (L)- and right (R)-handed circularly polarized light upon photon or electron excitation. Generally, an outstanding CPL-active material needs to possess a high luminescence dissymmetry factor (glum) (defined as 2(IL - IR)/(IL + IR) where I is the emission intensity), which is between -2 and +2. Although the exciting development in CPL-active materials was achieved, the modulation of CPL signs is still a challenge. For small organic systems, a relatively small glum value, one of the key parameters of CPL, limits their practical applications. Searching for efficient approaches for amplifying glum is important. Therefore, over the past decades, besides optimizing the structure of small molecules, many other strategies to obtain efficient CPL-active materials have been developed. For instance, self-assembly has been well demonstrated as an effective approach to amplify the supramolecular chirality as well as the glum values. On the other hand, chiral liquid crystals (CLCs), which are capable of selective reflection of left- and right-handed circularly polarized light, also to serve as a host matrix for endowing guest emitters with CPL activity and high glum values. However, self-assembly focuses on modulating the conformation and spatial arrangement of chiral emitters. And the CPL of a luminophore-doped CLC matrix depends on the helix pitch and band gap positions. Lately, novel photophysical approaches to modulate CPL signs have gradually emerged.In this Account, we discuss the recent progress of excited-state-regulation involved CPL-active materials. The emergence, amplification, and inversion of CPL can be adjusted through regulation of the excited state of chiral emitters. For example, Förster resonance energy transfer (FRET) can amplify the glum values of chiral energy acceptors in chiral supramolecular assemblies. By combining the concepts of photon upconversion and CPL, high-energy upconverted circularly polarized emission was achieved under excitation of low-energy light, accompanied by an amplified glum. In addition, the organic systems with unpaired electrons, i.e., charge transfer (CT) system and open-shell π-radical, show favorable CPL properties, which can be flexibly tuned with an applied magnetic field. It should be noted that these photophysical process are associated with the excited state of chiral emitters. So far, while the main focus is on the regulation of the molecular and supramolecular nanostructures, direct regulation of the excited state of the chiral system will serve as a new platform to understand and regulate the CPL activity and will be helpful to develop smart chiroptical materials.

Helical Nanostructures with Circularly Polarized Luminescence from the Multicomponent Assembly of π-Conjugated N-terminal Amino Acids.

Self-assembled structures with circularly polarized luminescence (CPL) have attracted great attention in recent years. π-conjugated N-terminal amino acids with chiral amino acid residues and luminophores are capable of forming self-assembled structures at hierarchical levels, whereby chirality can be transferred to the macroscopic scale with easily modulated CPL properties. Due to the presence of multiple noncovalent binding sites, including hydrogen bonding and aromatic interactions, π-conjugated N-terminal amino acids are emerging core candidates for incorporation into multicomponent self-assembled architectures, accomplishing rational control over supramolecular chirality as well as showing rich chiroptical properties. In this Minireview, we provide a brief summary of multiple-component coassembled systems comprising π-conjugated N-terminal amino acids, small organic species and metal ions. The synthesis of helical structures and manipulation of supramolecular chirality by controlling the self-assembled species is introduced, and the CPL properties of multiple-component π-conjugated N-terminal amino acids are also briefly summarized.

Rational Design of the Platinahelicene Enantiomers for Deep-Red Circularly Polarized Organic Light-Emitting Diodes.

[n]Helicene derivatives are most popular chiral structures to construct luminescent materials with circularly polarized (CP) light, which have revealed appealing application in chiral optoelectronics. Particularly, because of the unique phosphorescent emission, platinahelicene has great application prospects in CP organic light-emitting diode (CP-OLED). Herein, by decorating the pyridinyl-helicene ligand with trifluoromethyl (-CF3) unit in a specific position, a pair of platinahelicene enantiomers was prepared and separated with extremely twisted structure showing not only superior thermal and configurational stability but also good CP luminescence (CPL) property with dissymmetry factors (|gPL|) of 6 × 10−3. Moreover, the evaporated CP-OLEDs based on platinahelicene enantiomers exhibited the deep-red emission with the peak at 653 nm as well as obvious CP electroluminescence (CPEL) signals with the |gEL| in 10−3 order. Therefore, the design strategy provides an efficient way to improve the CPL properties of platinahelicene to cope with the future application in CP-OLEDs.

Simple Perylene Diimide Cyclohexane Derivative With Combined CPL and TPA Properties.

In this work we describe the linear and non-linear (chiro)optical properties of an enantiopure bis-perylenediimide (PDI) cyclohexane derivative. This compound exhibits upconversion based on a two-photon absorption (TPA) process with a cross-section value of 70 GM together with emission of circularly polarized luminescence (CPL), showing a glum in the range of 10−3. This simple structure represents one of the scarce examples of purely organic compounds combining both TPA and CPL responses, together with large values of molar absorptivity and fluorescence quantum yield with emission in the 500–600 nm. Self-assembly induced by introduction of a poor solvent allows for a spectacular shift of the emission into the near-infrared (NIR, 650–750 nm) by formation of well-defined rotationally displaced dimers. Therefore, we are here presenting a versatile platform whose optical properties can be simply tuned by self-assembly or by functionalization of the electron-deficient aromatic core of PDIs.

Chiral thermally activated delayed fluorescence emitters with dual conformations based on a pair of enantiomeric donors containing asymmetric carbons

Thermally activated delayed fluorescence (TADF) chiral emitters attract widespread attention due to their high exciton utilization as well as potential applications. In this work, we developed a pair of chiral donors, (R) and (S)-9-methyl-2,9-diphenyl-9,10-dihydroacridine (PMAc), for general TADF molecular design. The enantiomers (R) and (S)-TTR-PMAc are accordingly constructed. Interestingly, they are not only TADF emitters, but also possess dual stable conformations, i.e. nearly planar and nearly orthogonal conformations. (R) and (S)-TTR-PMAc show similar physical properties under conventional non-polarized environment. While under chiroptical environments, they exhibit obvious mirror-like circular dichroism (CD) and circularly polarized luminescence (CPL) properties. Moreover, by further comparing the CPL properties originated from each conformer, we confirm that molecular conformations can significantly influence the chiroptical performance.

Progress in Atomically Precise Coinage Metal Clusters with Aggregation‐Induced Emission and Circularly Polarized Luminescence

AbstractMaterials with circularly polarized luminescence (CPL) are especially fascinating due to the widespread potential applications in 3D displays, biological probes, security encoding, encrypted information transmission, and storage. Among these CPL‐active materials, the ones based on atomically precise coinage, namely, the metal coinage clusters, have attracted increasing attention due to their fascinating chiral structures and intriguing luminescence characteristics. Meanwhile, these clusters provide an ideal platform at the nanoscale for understanding the chiral transfer across the organic–inorganic interface. In this report, the recent progress in constructing enantiomerically pure chiral coinage metal clusters and the luminescent mechanism of coinage metal clusters in aggregated state are reviewed, respectively. Moreover, CPL‐active atomically precise coinage metal clusters and their design strategies are discussed in detail. Finally, challenges and opportunities for constructing atomically precise coinage metal clusters with excellent CPL properties are discussed.

Circularly polarized luminescence of nanoassemblies via multi-dimensional chiral architecture control.

Circularly polarized luminescence (CPL) materials are currently an important class of chiroptical materials that are attracting increasing interest. Nanoassemblies constructed from chiral or achiral building blocks show great potential for achieving CPL-active nanomaterials with high quantum yields and dissymmetry factors, which is crucial for further applications. In nanoassemblies, the dimensional morphology affects the chiroptical properties significantly since the microscopic packing modes will affect the luminescence processes and chirality transfer processes. In this review, we will show some examples for illustrating the relationship between multi-dimensional morphology and chiroptical properties. Furthermore, with dimensional morphology tuning, higher dissymmetry factors would be obtained. We hope to provide a useful and powerful insight into the design and control of CPL-active nanoassemblies via morphology control.

A Highly Luminescent Chiral Tetrahedral Eu4L4(L')4 Cage: Chirality Induction, Chirality Memory, and Circularly Polarized Luminescence.

Chiral lanthanide cages with circularly polarized luminescence (CPL) properties have found potential application in enantioselective guest recognition and sensing. However, it still remains a big challenge to develop a simple and robust method for the diastereoselective assembly of homochiral lanthanide cages in view of the large lability of the Ln(III) ions. Herein, we report the first example of the formation of a enantiopure lanthanide tetrahedral cage via a chiral ancillary ligand induction strategy. One such cage, (Eu4L4)(R/S-BINAPO)4, is assembled by four achiral C3-symmeric tris(β-diketones) (4,4',4″-tris(4,4,4-trifluoro-1,3-dioxobutyl)triphenylamine, L) as faces, four Eu(III) ions as vertices and four chiral R-/S-bis(diphenylphosphoryl)-1,1'-binaphthyl (R/S-BINAPO) as ancillary ligands. X-ray crystallography and NMR and CD spectra confirm the formation of a pair of enantiopure chiral topological tetrahedral cages, (Eu4L4)(R-BINAPO)4 and (Eu4L4)(S-BINAPO)4 (ΔΔΔΔ-1 and ΛΛΛΛ-1). As expected, the tetrahedral cages present strong CPL with |glum| values up to 0.20, while they unexpectedly give ultrahigh luminescent quantum yields (QYs) of up to 81%, the highest value reported in chiral Ln(III) complexes. More impressively, the chiral memory effect for a lanthanide-based assembly is observed for the first time. The chirality of the original cage 1 framework is retained after R/S-BINAPO is replaced by the achiral bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO), and thus another pair of enantiopure Eu(III) tetrahedral cages, ΔΔΔΔ- and ΛΛΛΛ-[(Eu4L4)(DPEPO)4] (ΔΔΔΔ-2 and ΛΛΛΛ-2), have been isolated. Encouragingly, cage 2 also presents an impressive luminescence quantum yield (QY = 68%) and intense CPL (|glum| = 0.11). This study offers a simple and low-cost synthesis strategy for the preparation of lanthanide cages with CPL properties.

Liquid-Phase Epitaxial Growth of Azapyrene-Based Chiral Metal-Organic Framework Thin Films for Circularly Polarized Luminescence.

Development of chiral metal-organic frameworks (MOFs) for circularly polarized luminescence (CPL) is a challenging but important task. In this work, we report a first example of azapyrene-based chiral MOF thin films [Zn2Cam2DAP]n grown on functionalized substrates (named SURchirMOF-4) for CPL property. By using a liquid-phase epitaxial layer-by-layer method, the resulted SURchirMOF-4 was constructed from chiral camphoric acid and 2,7-diazapyrene ligand, which has high orientation and homogeneity. The circular dichroism, CPL, and enantioselective adsorption results show that SURchirMOF-4 has strong chirality and CPL property as well as good enantioselective adsorption toward enantiomers of methyl-lactate. The synthesis of azapyrene-based chiral MOF thin films not only represents an ideal model for studying the enantioselective adsorption, but also will be a valuable approach for development of the chiral thin film exhibiting CPL property.

Construction of Chiral Nanoassemblies Based on Host-Guest Complexes and Their Responsive CD and CPL Properties: Chirality Transfer From 2,6-helic[6]arenes to a Stilbazolium Derivative.

A couple of water-soluble chiral 2,6-helic[6]arene derivatives P-H1 and M-H1 were synthesized, and they could form 1:1 stable complexes with 4-[(4′-N, N-diphenylamino)-styryl]-N-methylpyridinium iodide (G) in water. Compared with G, the host-guest complexes exhibited enhanced fluorescence, which might be attributed to the spatial confinement of G and restriction of aggregation-caused quenching (ACQ) effects. Based on the host-guest complexation, the first helic[6]arene-based chiral assemblies were then constructed, and they showed rectangular or hexagonal nanostructures by scanning electron microscopy (SEM) images. Interestingly, the assemblies showed clear mirror-image circular dichroism (CD) and circularly polarized luminescence (CPL) spectra in aqueous solution, revealing a consecutive chirality transfer from the chiral macrocyclic cavities of the hosts to G. Moreover, the supramolecular chirality of the assemblies could also show responsiveness to the pH values and temperatures of the system.