Oxidation of an Internal-Edge-Substituted [5]Helicene-Derived Phosphine Synchronously Enhances Circularly Polarized Luminescence

Small chiral organic molecules with CD properties are in high demanded due to their potential use in promising electronic and biological applications. Herein, we reveal a system in which the oxidation of a phosphino group to the corresponding phosphine oxide on the inner rim of a helicene derivative induces a CPL response. Laterally π-extended 7,8-dihydro[5]helicenes bearing phosphine and phosphine oxide groups on their inner helical rims (i. e., the C1 position) were synthesized, and their helical structures were unambiguously determined by X-ray crystallography. The photophysical (UV/visible and emission) and chiroptical properties of these compounds were investigated in various solvents. Despite their structural similarities, phosphine oxide showed a significantly better CPL response than phosphine, with a high dissymmetry factor for emission (|g_lum|=(1.3–1.9)×10⁻³) that can be attributed to structural changes in the interior of the helicene helix.     

Cyclobishelicenes: Shape-Persistent Figure-Eight Aromatic Molecules with Promising Chiroptical Properties

Cyclobis[n]helicenes (n=3 or 5) are chiral D₂-symmetric π-conjugated macrocycles with stable lemniscular, or figure-eight, shapes. The conformational analysis of five different cyclobis[n]helicenes revealed that these molecules can only exist as their lemniscular conformers with high barriers to enantiomerization (>200 kJ mol⁻¹). The enantiomers of a cyclobis[5]helicene were resolved by HPLC and their unusual chiroptical properties were attributed to the inherent chirality of their macrocyclic figure-eight.     

Synthesis and Chiroptical Properties of Quinoxaline-Fused Polyaza[5]–[7]helicenes with Orange-Color CPL Emissions

We achieved a two-type synthesis of quinoxaline-fused polyaza[5]- and [7]helicenes through consecutive N−H/C−H coupling with a hypervalent iodine reagent as a key reaction. By fusing electron-deficient quinoxaline, these polyazahelicenes constitute an efficient donor-acceptor type of molecule with absorption edges that reach up to approximately 650 nm. Evaluating the chiroptical properties reveals that the polyazahelicene exhibits a rare orange circularly polarized glow with a luminescence dissymmetry factor (g_lum value) of 0.003.     

Synthesis of Highly Luminescent Chiral Nanographene

Chiral nanographenes with both high fluorescence quantum yields (Φ_F) and large dissymmetry factors (g_lum) are essential to the development of circularly polarized luminescence (CPL) materials. However, most studies have been focused on the improvement of g_lum, whereas how to design highly emissive chiral nanographenes is still unclear. In this work, we propose a new design strategy to achieve chiral nanographenes with high Φ_F by helical π-extension of strongly luminescent chromophores while maintaining the frontier molecular orbital (FMO) distribution pattern. Chiral nanographene with perylene as the core and two dibenzo[6]helicene fragments as the wings has been synthesized, which exhibits a record high Φ_F of 93 % among the reported chiral nanographenes and excellent CPL brightness (B_CPL) of 32 M⁻¹ cm⁻¹.     

Synthesis of a π-Extended Double [9]Helicene

Double helicenes are appealing chiral frameworks. Their π-extension is desirable to achieve (chir)optical response in the visible and near-infrared (NIR) region, but access to higher double [n]helicenes (n≥8) has remained challenging. Herein, we report an unprecedented π-extended double [9]helicene ( D9H ), unambiguously revealing its structure by single-crystal X-ray diffraction. D9H shows remarkable NIR emission from 750 to 1100 nm with a high photoluminescence quantum yield of 18 %. In addition, optically pure D9H exhibits panchromatic circular dichroism with a notable dissymmetry factor (g_CD) of 0.019 at 590 nm, which is among the highest in the visible region for reported helicenes.     

Helically Assembled Pyrene Arrays on an RNA Duplex That Exhibit Circularly Polarized Luminescence with Excimer Formation

Circularly polarized luminescence (CPL) was observed in pyrene zipper arrays helically arranged on an RNA duplex. Hybridization of complementary RNA strands having multiple (two to five) 2′‐O‐pyrenylmethyl modified nucleosides affords an RNA duplex with normal thermal stability. The pyrene fluorophores are assembled like a zipper in a well‐defined helical manner along the axis of RNA duplex, which, upon 350 nm UV illumination, resulted in CPL emission with pyrene excimer formation. CPL (g_lum) levels observed for the pyrene arrays in dilute aqueous solution were +2×10^?2–+3.5×10^?2, which are comparable with |g_lum| for chiral organic molecules and related systems. The positive CPL signals are consistent with a right‐handed helical structure. Temperature dependence on CPL emission indicates that the stable rigid RNA structure is responsible for the strong CPL signals. The single pyrene‐modified RNA duplex did not show any CPL signal.     

Multiple Fused Anthracenes as Helical Polycyclic Aromatic Hydrocarbon Motif for Chiroptical Performance Enhancement

Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π‐conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt‐catalyzed cycloisomerization of the corresponding ethynyl‐substituted precursors. The nonplanar and helical structure was confirmed by X‐ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol^?1. The enantiomers of the diphenyl derivative were successfully resolved by chiral HPLC. Enantiopure samples showed good chiroptical performance in the CD (|Δ?| 1380 L mol^?1 cm^?1) and CPL (|g_lum| 0.013) spectra, and these values were considerably large for simple organic molecules. The unique chiroptical properties are discussed on the basis of the molecular structure and the electronic state with the aid of time‐dependent DFT calculations.     

Synthesis of Terminally Fluorinated [7]Helicenes and Their Application to Photochemical Domino Reactions

The intramolecular Diels−Alder reactions of helicenes deform their π-conjugated screw-shaped skeletons. In particular, terminally tetrafluorinated [7]helicene (F₄-[7]helicene) undergoes a photoinduced Diels−Alder reaction followed by a photoinduced double fluorine atom transfer. Herein, we thoroughly investigated this photochemical domino process by decreasing the level of fluorine substitution. F₃-[7]Helicenes bearing two fluorine atoms at the dienophile terminal underwent photoinduced Diels−Alder reactions, but the whole domino process became slow. F₂-[7]Helicene, which is difluorinated only at the dienophile terminal, was also photolabile. As a result, two fluorine atoms were sufficient for the photochemical domino reaction to occur. X-ray crystallographic analysis revealed that F₂-[7]helicene was less compressed than F₄-[7]helicene, indicating that terminal polyfluorination enhanced the intramolecular arene−fluoroarene stacking interactions and thus promoted the transformations.     

Selective Synthesis of Conjugated Chiral Macrocycles: Sidewall Segments of (−)/(+)-(12,4) Carbon Nanotubes with Strong Circularly Polarized Luminescence

Carbon nanotubes (CNTs) have unusual physical properties that are valuable for nanotechnology and electronics, but the chemical synthesis of chirality- and diameter-specific CNTs and π-conjugated CNT segments is still a great challenge. Reported here are the selective syntheses, isolations, characterizations, and photophysical properties of two novel chiral conjugated macrocycles ([4]cyclo-2,6-anthracene; [4]CAn_2,6 ), as (−)/(+)-(12,4) carbon nanotube segments. These conjugated macrocyclic molecules were obtained using a bottom-up assembly approach and subsequent reductive elimination reaction. The hoop-shaped molecules can be directly viewed by a STM technique. In addition, chiral enantiomers with (−)/(+) helicity of the [4]CAn_2,6 were successfully isolated by HPLC. The new tubular CNT segments exhibit large absorption and photoluminescence redshifts compared to the monomer unit. The carbon enantiomers are also observed to show strong circularly polarized luminescence (g_lum≈0.1). The results reported here expand the scope of materials design for bottom-up synthesis of chiral macrocycles and enrich existing knowledge of their optoelectronic properties.     

A π-Extended Pentadecabenzo[9]Helicene

A novel chiral nanographene (i.e. EP9H ) with a pentadecabenzo[9]helicene core fragment has been synthesized and fully characterized. Single-crystal X-ray diffraction unambiguously confirms the helical structure. The fluorescence emission of EP9H is located in the near infrared region (λ_em=684 nm) with a medium quantum yield (0.10) for helicene derivatives. Cyclic voltammetry reveals its seven quasi-reversible redox states from −2 to +5. Furthermore, enantiopure EP9H displays distinct CD signals in a broad spectral range from 300 to 700 nm. Notably, compared to the reported small organic molecules, EP9H displays an outstanding |g_lum| value of 4.50×10⁻² and B_CPL as 304 M⁻¹ cm⁻¹.     

Experimental and Theoretical Structure Elucidation of the [2 : 1] Complex Ion of Carbo[n]helicene with n=6, 7 and 8 and Ag+

Gas-phase complexes of [n]helicenes with n=6, 7 and 8 and the silver(I) cation are generated utilizing electrospray ionization mass spectrometry (ESI-MS). Besides the well-established [1 : 1] helicene/Ag⁺-complex in which the helicene provides a tweezer-like surrounding for the Ag⁺, there is also a [2 : 1] complex formed. Density functional theory (DFT) calculations in conjunction with energy-resolved collision-induced dissociation (ER-CID) experiments reveal that the second helicene attaches via π-π stacking to the first helicene, which is part of the pre-formed [1 : 1] tweezer complex with Ag⁺. For polycyclic aromatic hydrocarbons (PAHs) of planar structure, the [2 : 1] complex with silver(I) is typically structured as an Ag⁺-bound dimer in which the Ag⁺ would bind to both PAHs as the central metal ion (PAH–Ag⁺–PAH). For helicenes, the Ag⁺-bound dimer is of similar thermochemical stability as the π-π stacked dimer, however, it is kinetically inaccessible. Coronene (Cor) is investigated in comparison to the helicenes as an essentially planar PAH. In analogy to the π-π stacked dimer of the helicenes, the Cor−Ag⁺−Cor−Cor complex is also observed. Competition experiments using [n]helicene mixtures reveal that the tweezer complexes of Ag⁺ are preferably formed with the larger helicenes, with n=6 being entirely ignored as the host for Ag⁺ in the presence of n=7 or 8.     

Rhodium-Catalyzed Enantioselective Synthesis of Highly Fluorescent and CPL-Active Dispiroindeno[2,1-c]fluorenes

The enantioselective synthesis of chiral [7]-helical dispirodihydro[2,1-c]indenofluorenes (DSF-IFs) was achieved for the first time in good yields with high er values (er up to 99 : 1). The crucial step of the whole reaction sequence was the enantioselective intramolecular [2+2+2] cycloaddition of tethered triynediols to indenofluorenediols, which was catalyzed by a Rh/SEGPHOS® complex. Further transformations led to the corresponding DSF-IFs. The prepared helically chiral DSF-IFs combine circularly polarized luminescence (CPL) activity (g_lum=∼10⁻³) with exceptionally high fluorescence quantum yields (up to Φ_lum=0.97).     

Axially Chiral TADF-Active Enantiomers Designed for Efficient Blue Circularly Polarized Electroluminescence

The use of a chiral, emitting skeleton for axially chiral enantiomers showing activity in thermally activated delayed fluorescence (TADF) with circularly polarized electroluminescence (CPEL) is proposed. A pair of chiral stable enantiomers, (−)-(S)-Cz-Ax-CN and (+)-(R)-Cz-Ax-CN, was designed and synthesized. The enantiomers, both exhibiting intramolecular π-conjugated charge transfer (CT) and spatial CT, show TADF activities with a small singlet–triplet energy difference (ΔE_ST) of 0.029 eV and mirror-image circularly polarized luminescence (CPL) activities with large g_lum values. Notably, CP-OLEDs based on the enantiomers feature blue electroluminescence centered at 468 nm with external quantum efficiencies (EQEs) of 12.5 and 12.7 %, and also show intense CPEL with g_EL values of −1.2×10⁻² and +1.4×10⁻², respectively. These are the first CP-OLEDs based on TADF-active enantiomers with efficient blue CPEL.     

Facile Two‐Step Synthesis of 1,10‐Phenanthroline‐Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency

A facile two‐step synthesis of aza[7]helicenes possessing a 6‐5‐6‐6‐6‐5‐6 skeleton from commercially available 2,9‐dichloro‐1,10‐phenanthroline via double amination with aniline derivatives followed by hypervalent iodine reagent‐mediated intramolecular double‐NH/CH couplings was developed. Single‐crystal X‐ray analyses of the helicenes revealed unique structures, including both a significantly twisted center and planar terminals of the skeleton. The azahelicenes show high fluorescent quantum yields (Φ s) under both neutral (Φ : 0.25–0.55) and acidic conditions (Φ : up to 0.80). An enantiomerically pure aza[7]helicene showed high circularly polarized luminescence (CPL) activity under both neutral and acidic conditions (g _lum: up to 0.009).     

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.     

Synthesis and Chiroptical Properties of Binaphthyl-Hinged [5]Helicenes

The synthesis, structure, and circularly polarized luminescence (CPL) of two types of shape-persistent [5]helicenes, hinged by a tethered (−OCH₂CH₂O−) or untethered (−OCH₃) binaphthyl, are reported. The binaphthyl tethering system facilitated an effective Wittig ring-closure reaction in the synthesis of a macrocyclic precursor, which could be easily converted to the title compound via successive photocyclization. The tethered groups were replaced with untethered −OCH₃ groups by treatment with BBr₃ followed by methylation. Both compounds exhibited similar spectra, and their longest wavelength absorption band with a low intensity was attributed to the transition from HOMO to LUMO+1. These compounds exhibited CPL with higher dissymmetry factors g_lum values than unlocked helicenes.     

Small Figure-Eight Luminophores: Double-Twisted Tethered Cyclic Binaphthyls Boost Circularly Polarized Luminescence

Double-twisted cyclic binaphthyls, in which two naphthalenes are tethered by -O(CH₂)_nO- linkage (n=1–3), have been synthesized. X-ray analyses and DFT calculations revealed a tightly constrained stereogenic figure-eight geometry. Tethering of two naphthalenes by short linkage forces a small dihedral angle, and the cyclic binaphthyls with short tether (n=1, 2) exhibit remarkable boosting of the g_lum value (1.0–1.6×10⁻²) in circularly polarized luminescence (CPL) and unusual g_lum/g_abs ratios (0.93–1.3). These experimental high |g_lum| values are in accord with the results of excited state TD-DFT calculations, which show transannular interactions and that consequent extensive delocalization occurs throughout the figure-eight π-core. As a result, the present figure-eight luminophore promote the elongation of the magnetic transition dipole moment that results in significant increases in g_lum values.     

Diastereoselective Strategies towards Thia[n]helicenes

In the present study, we have investigated different strategies for diastereoselective synthesis of thia[n]helicenes. We describe the introduction of different chiral auxiliaries at various positions and investigated their effect in the photocyclization reaction. Different chiral groups were placed at the sterically hindered position of the helical core and their interactions with various solvents and metals like copper were investigated. The use of Cu^I salts has led to high diastereoselectivity in the photocyclization process and we were successful in obtaining the thia[5]helicene in enantiomerically pure form in good yield. The single diastereomer obtained was characterized by X‐ray crystallography. From the study of the barrier of racemization of these thia[5]helicenes, the stability was found to be comparable to unsubstituted tetrathia[7]helicenes and substituted diazadithia[7]helicenes. This approach provides an easy access to enantiopure helicenes.     

A Doubly Alkynylpyrene‐Threaded [4]Rotaxane That Exhibits Strong Circularly Polarized Luminescence from the Spatially Restricted Excimer

The Sonogashira coupling of γ‐CD‐encapsulated alkynylpyrenes with terphenyl‐type stopper molecules gave a doubly alkynylpyrene‐threaded [4]rotaxane. The rotaxane showed only excimer emission, with a high fluorescence quantum yield of Φ_f=0.37, arising from the spatially restricted excimer within the cavity of the γ‐CD. The excimer emission suffered little from self‐quenching up to a concentration of 1.5×10^?5 M and was circularly polarized with a high g_lum value of ?1.5×10^?2. The strong circularly polarized luminescence may result from the two stacked pyrenes existing in the rotaxane in an asymmetrically twisted manner.     

Transformation of Thia[7]helicene to Aza[7]helicenes and [7]Helicene-like Compounds via Aromatic Metamorphosis

[n]Helicenes with helically twisted structures have attracted increasing interest owing to their unique properties. Therefore, it has been an important issue to develop facile synthetic methodologies which allow access to a variety of [n]helicenes. Here we report the synthesis of [7]helicenes and [7]helicene-like compounds from the thia[7]helicene as a common starting material. Desulfurative dilithiation of the thia[7]helicene and the subsequent reaction with silicon and phosphorus electrophiles afforded the silole- and phosphole-fused [7]helicene-like compounds, respectively. The cyclopentadiene-fused [7]helicene-like compound and the pyrrole-fused aza[7]helicenes were also successfully synthesized via twofold S_NAr reactions of the thia[7]helicene S,S-dioxide with the carbon and nitrogen nucleophiles, respectively. The thia[7]helicene S,S-dioxide showed a slightly red-shifted absorption spectrum than the parent thia[7]helicene, which was well demonstrated by the theoretical calculations. The substituents on the silicon atom of silole-fused [7]helicene-like compounds have little impact on the longest absorption maximum. Such little effect of the substituents on absorption properties was also observed for cyclopentadiene-fused [7]helicene-like compounds and aza[7]helicenes and was well demonstrated by the theoretical calculations. The thia[7]helicene S,S-dioxide and the silole-fused [7]helicene-like compound exhibited bright blue emission, and the cyclopentadiene-fused [7]helicene-like compound and the aza[7]helicenes showed strong violet emission. Each single enantiomer of the aza[7]helicenes showed circularly-polarized luminescence with the dissymmetry factors of 4.2~4.4 × 10⁻³.