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.     

Building Molecular Complexity from Quinizarin: Conjoined Coumarins and Coronene Analogs

The double Knoevenagel condensation of 1,4‐dibenzoyloxyanthraquinone with methyl esters of arylacetic acids affords a series of compounds based upon a previously unknown 1,8‐dioxa‐benzo[e]pyrene‐2,7‐dione heterocyclic core. The aryl groups incorporated in the 3‐ and 6‐positions can be oxidatively coupled to the π‐expanded backbone to produce a further new heterocyclic core: 1,10‐dioxa‐dibenzo[dj]coronene‐2,9‐dione. The intriguing optical properties of these π‐expanded coumarin derivatives are discussed and rationalized through quantum chemical calculations. The broad absorption bands of 1,8‐dioxa‐benzo[e]pyrene‐2,7‐dione‐based dyes are attributed to both HOMO?1→LUMO and HOMO→LUMO transitions, which have a similar energy. Weakly coupled electron‐donating aryl substituents result in a moderate bathochromic shift of both the absorption and emission by 30–60 nm in toluene. The emissive properties of these compounds are in part determined by the oscillator strength of the main transition, lifetimes of the excited state, and by the energy match of the excited state with a triplet state of a similar energy. The 1,10‐dioxa‐dibenzo[dj]coronene‐2,9‐dione displays a much smaller Stokes shift, yet a markedly increased fluorescence quantum yield of 90 % owing to the increased rigidity compared with the 1,8‐dioxa‐benzo[e]pyrene‐2,7‐dione core.     

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.     

Dual Upconverted and Downconverted Circularly Polarized Luminescence in Donor–Acceptor Assemblies

Through mimicking both the chiral and energy transfer in an artificial self‐assembled system, not only was chiral transfer realized but also a dual upconverted and downconverted energy transfer system was created that emit circularly polarized luminescence. The individual chiral π‐gelator can self‐assemble into a nanofiber exhibiting supramolecular chirality and circularly polarized luminescence (CPL). In the presence of an achiral sensitizer Pd^II octaethylporphyrin derivative, both chirality transfer from chiral gelator to achiral sensitizer and triplet‐triplet energy transfer from excited sensitizer to chiral gelator could be realized. Upconverted CPL could be observed through a triplet–triplet annihilation photon upconversion (TTA‐UC), while downconverted CPL could be obtained from chirality‐transfer‐induced emission of the achiral sensitizer. The interplay between chiral energy acceptor and achiral sensitizer promoted the communication of chiral and excited energy information.     

Red Emissive Double Aza[7]helicenes with Antiaromaticity / Aromaticity Switching via the Redox-Induced Radical Cation and Dication Species

We herein present the synthetic approach to a new antiaromatic double aza[7]helicene C that features NN-embedded polycyclic aromatic hydrocarbons (PAHs). This heteroatom-doped helicene showed a rarely obtained long-wavelength emission and far-red circularly polarized luminescence (CPL) in the solid state. These optical and chiroptical properties could be ascribed to both the NN-PAH core structure and the further extension through angular ring fusions. Such a unique electronic structure also culminated in facile chemical oxidations of neutral C to the positively charged chiral radical ( C ⋅⁺) and dication species ( C ²⁺). Interestingly, DFT computations revealed that the pyridazine central core showed an antiaromaticity-to-aromaticity switching, in contrast to the inversed transition for the helical periphery in cationic states. The reported approaches are anticipated to lead to the development of further redox-active chiral systems for potential applications in chiroptoelectronics, spintronics as well as fluorescent bioimaging.     

Long‐Lived Circularly Polarized Phosphorescence in Helicene‐NHC Rhenium(I) Complexes: The Influence of Helicene,Halogen, and Stereochemistry on Emission Properties

The first enantiopure chiral‐at‐rhenium complexes of the form fac‐ReX(CO)₃(:C^N) have been prepared, where :C^N is a helicene‐N‐heterocyclic carbene (NHC) ligand and X=Cl or I. These have complexes show strong changes in the emission characteristics, notably strongly enhanced phosphorescence lifetimes (reaching 0.7 ms) and increased circularly polarized emission (CPL) activity, as compared to their parent chiral models lacking the helicene unit. The halogen along with its position within the dissymmetric stereochemical environment strongly affect the photophysics of the complexes, particularly the phosphorescence quantum yield and lifetime. These results give fresh insight into fine tuning of photophysical and chiroptical properties of Re‐NHC systems.     

Tuning of Supramolecular Architectures of l‐Valine‐Containing Dicyanoplatinum(II) 2,2′‐Bipyridine Complexes by Metal–Metal, π–π Stacking,and Hydrogen‐Bonding Interactions

A series of newly synthesized dicyanoplatinum(II) 2,2′‐bipyridine complexes exhibits self‐assembly properties in solution after the incorporation of the l ‐valine amino units appended with various hydrophobic motifs. These l ‐valine‐derived substituents were found to have critical control over the aggregation behaviors of the complexes in the solution state. On one hand, one of the complexes was found to exhibit interesting circularly polarized luminescence (CPL) signals at low temperature due to the formation of chiral spherical aggregates in the temperature‐dependent studies. On the other hand, systematic transformation from less uniform aggregates to well‐defined fibrous and rod‐like structures via Pt???Pt and π–π stacking interactions has also been observed in the mixed‐solvent studies. These changes were monitored by UV/Vis absorption, emission, circular dichroism (CD), and CPL spectroscopies, and morphologies were studied by electron microscopy.     

Mechanochromic luminescence of soft crystals: Recent systematic studies in controlling the molecular packing and mechanoresponsive properties

Soft crystals are a class of smart materials that can switch their photophysical or mechanical properties in response to gentle external stimuli. A representative stimuli-responsive behavior of soft crystals is mechanochromic luminescence (MCL), i.e., a reversible color change of solid-state photoluminescence induced by external mechanical stimuli. Together with the rapid growth in the area of solid-state photoluminescence including fluorescence, room-temperature phosphorescence (RTP), thermally activated delayed fluorescence (TADF), white-light emission (WLE), and circularly polarized luminescence (CPL), a number of soft crystals that exhibit MCL behaviors have been reported during the past decade. In the typical MCL of soft crystals, the emission color switches in the bathochromic direction upon amorphization by grinding and recovers to the original color upon recrystallization by heating or exposure to organic solvents. Relatively few are known to exhibit hypsochromically shifted MCL, two-step MCL, self-recovering MCL, or mechanical-stimuli-induced single-crystal-to-single-crystal (SCSC) transitions. Rational design guidelines to control the mechanoresponsive properties of soft crystals have not yet been established. This review summarizes the systematic studies on the substituent effect to control the MCL properties of soft crystals. Recent studies provide useful insights into the effects of electronic and steric differences of substituents on crystal structure, luminescence properties, and mechanoresponsive behaviors.     

Azahelicene‐Fused BODIPY Analogues Showing Circularly Polarized Luminescence

Helical carbazole‐based BODIPY analogues were readily synthesized via aza[7]helicenes. The structures of azahelicene‐incorporated BF₂ dyes were elucidated by x‐ray diffraction analysis. DFT calculations revealed that the π‐conjugated system expanded from the helicene moiety to the BODIPY framework. The azahelicene‐fused boron complexes showed the Cotton effects and the circularly polarized luminescence (CPL) in the visible region. Furthermore, an axially chiral binaphthyl group was attached to the helically chiral dyes, which enhanced the chiroptical properties.     

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.     

One-Step Simultaneous Synthesis of Circularly Polarized Luminescent Multiple Helicenes Using a Chrysene Framework

A series of multiple helicenes was simultaneously synthesized in one step by intramolecular cyclization of a single chrysene derivative containing two 2-[(4-alkoxyphenyl)ethynyl]phenyl units accompanied by rearrangements of the aryl pendants. The electrophile-induced double cyclization with or without aryl migrations proceeded efficiently under acidic conditions to afford annulative π-extension of the chrysene units and produced quadruple (QH- 2 ), triple (TH- 2 ), and double (DH- 2 ) helicenes containing [4]- and/or [5]helicene frameworks with dynamic and/or static helicene chirality in one step. Three multiple helicenes’ structures were determined by X-ray crystallography and/or density functional theory calculations. The multiple TH- 2 and DH- 2 helicenes were separated into enantiomers because of the stable one and two [5]helicene moieties, respectively, and showed intense circular dichroism and circularly polarized luminescence. Although QH- 2 , which comprises four [4]helicene subunits, was not resolved into enantiomers, the TH- 2 enantiomers were further separated into a pair of diastereomers at low temperature resulting from their substituted [4]helicene chirality.     

Synthetic Control of the Excited‐State Dynamics and Circularly Polarized Luminescence of Fluorescent “Push–Pull” Tetrathia[9]helicenes

A series of fluorescent “push‐pull” tetrathia[9]helicenes based on quinoxaline (acceptor) fused with tetrathia[9]helicene (donor) derivatives was synthesized for control of the excited‐state dynamics and circularly polarized luminescence (CPL) properties. In this work, introduction of a quinoxaline onto the tetrathia[9]helicene skeleton induced the “push–pull” character, which was enhanced by further introduction of an electron‐releasing Me₂N group or an electron‐withdrawing NC group onto the quinoxaline unit (denoted as Me₂N‐QTTH and NC‐QTTH, respectively). These trends were successfully discussed in terms of by electrochemical measurements and density functional theory (DFT) calculations. As a consequence, significant enhancements in the fluorescence quantum yields (Φ_FL) were achieved. In particular, the maximum Φ_FL of Me₂N‐QTTH was 0.43 in benzene (NC‐QTTH: Φ_FL=0.30), which is more than 20 times larger than that of a pristine tetrathia[9]helicene (denoted as TTH; Φ_FL=0.02). These enhancements were also explained by kinetic discussion of the excited‐state dynamics such as fluorescence and intersystem crossing (ISC) pathways. Such significant enhancements of the Φ_FL values thus enabled us to show the excellent CPL properties. The value of anisotropy factor g_CPL (normalized difference in emission of right‐handed and left‐handed circularly polarized light) was estimated to be 3.0×10^?3 for NC‐QTTH.     

Synthesis,Structure, and Properties of Near‐Infrared [b]Phenanthrene‐Fused BF2 Azadipyrromethenes

A new class of phenanthrene‐fused BF₂ azadipyrromethene (azaBODIPY) dyes have been synthesized through a tandem Suzuki reaction and oxidative ring‐fusion reaction, or a palladium‐catalyzed intramolecular C−H activation reaction. These phenanthrene‐fused azaBODIPY dyes are highly photostable and display markedly redshifted absorption (up to λ =771 nm) and emission bands (λ ≈800 nm) in the near‐infrared region. DFT calculations and cyclic voltammetry studies indicate that, upon annulation, more pronounced stabilization of the LUMO is the origin of the bathochromic shift of the absorption and high photostability.     

CIRCULAR POLARIZATION OF FLUORESCENCE EMITTED BY AN OPTICALLY ACTIVE COMPOUND

C hiral compounds absorb circularly polarized light of opposite sense to different extents. This property, commonly known as circular dichroism, CD, is closely related to the optical rotatory dispersion of the compound under study, and has been extensively applied to the study of chiral compounds[1, 2]. On the other hand, very little information is available concerning the preferential emission of circularly polarized light of one sense over that of the opposite sense from chiral luminescent compounds. The scarcity of data about circularly polarized luminescence, CPL, is probably due to lack of suitable instrumentation for the measurement of small amounts of circularly polarized light present in a large background of unpolarized luminescence. Indeed, the only CPL data available are of a few substances which exhibit an exceptionally high degree of circular polarization in their emitted light [3, 4].     

Lasing from an Organic Micro‐Helix

Organic solid‐state semiconductor lasers are attracting ever‐increasing interest for their potential application in future photonic circuits. Despite the great progress made in recent years, an organic laser from 3D chiral structures has not been achieved. Now, the first example of an organic nano‐laser from the micro‐helix structure of an achiral molecule is presented. Highly regular micro‐helixes with left/right‐handed helicity from a distyrylbenzene derivative (HM‐DSB) were fabricated and characterized under microscope spectrometers. These chiral micro‐helixes exhibit unique photonic properties, including helicity‐dependent circularly polarized luminescence (CPL), periodic optical waveguiding, and length‐dependent amplified spontaneous emission (ASE) behavior. The successful observation of laser behavior from the organic micro‐helix extends our understanding to morphology chirality of organic photonic materials and provides a new design strategy towards chiral photonic circuits.     

Controlling the Emissive,Chiroptical, and Electrochemical Properties of Double [7] Helicenes through Embedded Aromatic Rings

We present here the synthesis and in-depth physicochemical characterization of a double hetero[7]helicene fused with four triazole rings at both helical ends. The comparison of this triazole-fused double helicene with the previously reported all-carbon and thiadiazole-fused analogs revealed the huge impact of the embedded aromatic rings on the photophysical features. The small structural variation of the terminal rings from thiadiazole to triazole caused a dramatic change of the photoluminescence quantum yields (PLQYs) from <1 % to 96 %, while the replacement of the terminal benzene rings with triazole rings induced a tenfold enhancement of the circularly polarized luminescence dissymmetry factor. These observations were well corroborated with transient absorption analysis and/or theoretic calculations. In addition, the triazole-fused double helicene exhibited ambipolar redox behavior, enabling the generation of radical cation and anion species by electrochemical and chemical methods and showing its potential for spin-related applications.     

Recent Advancements in and the Future of Organic Emitters: TADF‐ and RTP‐Active Multifunctional Organic Materials

Organic emitting compounds that are based on π‐conjugated skeletons have emerged as promising next‐generation materials for application in optoelectronic devices. In this Minireview, recent advances in the development of organic emitters that irradiate room‐temperature phosphorescence and/or thermally activated delayed fluorescence with extraordinary luminescence properties, such as aggregation‐induced emission, mechanochromic luminescence, and circularly polarized luminescence, are discussed.     

Intermolecular Charge-Transfer Luminescence by Self-Assembly of Pyridinium Luminophores in Solutions

Designing a luminophore for application both in solution and in the solid state is a highly challenging task given the distinct nature of intermolecular interactions in these phases. In this context, we demonstrate that self-assembly of non-emissive charged pyridinium luminophores enables luminescence in solutions through a mechanism that is characteristic for the crystal state. Specifically, protonation of pyridine luminophore subunits in a solution promotes oligomer formation through intermolecular π⁺-π interactions, leading to an intermolecular charge-transfer type luminescence. The luminescence turn-on by protonation is utilized for a highly efficient solution-state luminescent sensing of hydrogen chloride and sulfonic acids (TfOH, TsOH and MsOH) with detection limits spanning the range from 0.06 to 0.33 ppm. The protonation followed by self-assembly results in a bathochromic shift of the emission from 420 nm to 550 nm.     

Synthesis and characterization of near-infrared absorbing benzannulated aza-BODIPY dyes

A series of novel aza‐diisoindolmethine dyes 9 with six different aryl and heteroaryl groups at the indole moiety have been synthesized by the addition of aryl Grignard compounds to phthalodinitrile and subsequent reaction with formamide. A plausible reaction mechanism, through a Leuckart–Wallach‐type reduction has been confirmed by means of DFT calculations of the related transition and intermediate states. The corresponding boron difluoride complexes ( 10) of 9 were prepared in a subsequent reaction step and the spectroscopic and electrochemical properties of 9 and 10 have been investigated both experimentally and theoretically. The aza‐diisoindolmethines 9 exhibit an absorption maximum in the range from 615 to 720 nm, whereas the complexes 10 show a bathochromically shifted absorption maximum between 681 and 793 nm. Measurements of 9 and 10 by cyclic voltammetry display fully reversible redox waves for the reduction and oxidation with higher potentials for 10 . From the measured redox potentials, the HOMO and LUMO energy levels were calculated for 9 and 10 . The frontier orbital energies, the energies of the absorption bands, as well as the orbitals involved in the absorption process were calculated with DFT and compared to the measured results of 9 and 10 . The absorption maximum can be related to an intense HOMO–LUMO transition and the more‐pronounced stabilization of the LUMO upon complexation is the origin of the bathochromic shift of the absorption. Additionally, single‐crystal structures for two species, 10 d and 10 f , are reported.     

Solvent polarity driven helicity inversion and circularly polarized luminescence in chiral aggregation induced emission fluorophores

Development of functional materials capable of exhibiting chirality tunable circularly polarized luminescence (CPL) is currently in high demand for potential technological applications. Herein we demonstrate the formation of both left- and right-handed fluorescent helical superstructures from each enantiomer of a chiral tetraphenylethylene derivative through judicious choice of the solution processing conditions. Interestingly, both the aggregation induced emission active enantiomers exhibit handedness inversion of their supramolecular helical assemblies just by varying the solution polarity without any change in their molecular chirality. The resulting helical supramolecular aggregates from each enantiomer are capable of emitting circularly polarized light, thus enabling both right- and left-handed CPL from a single chiral material. The left- and right-handed supramolecular helical aggregates in the dried films have been characterized using spectroscopy, scanning electron microscopy, and transmission electron microscopy techniques. These new chiral aggregation induced emission compounds could find applications in devices where CPL of opposite handedness is required from the same material and would facilitate our understanding of the formation of helical assemblies with switchable supramolecular chirality.

The formation of both left- and right-handed helical superstructures with circularly polarized luminescence has been achieved in a chiral tetraphenylethylene derivative just by varying the solution polarity without any change in molecular chirality.