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.     

NIR-Circularly Polarized Luminescence from Chiral Complexes of Lanthanides and d-Metals

In recent years, circularly polarized luminescence (CPL) has witnessed a renaissance, due to the increased popularity of CPL as a spectroscopic technique and greater accessibility to instrumentation. New efficient CPL emitters have been designed and many applications, ranging from electronic devices to microscopy have been proposed. Most examples of CPL are within the visible range, while few cases of near infrared (NIR) CPL active complexes are available. NIR-CPL compounds may have applications in the telecommunication industry, electronic devices and bioassays. In the following, we shall give an overview of the recent developments allowing for the measurements of NIR-CPL, and describe the chiroptical properties of metal complexes which achieve this feat.     

Planar Chiral Multiple Resonance Thermally Activated Delayed Fluorescence Materials for Efficient Circularly Polarized Electroluminescence

Chiral boron/nitrogen doped multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters are promising for highly efficient and color-pure circularly polarized organic light-emitting diodes (CP-OLEDs). Herein, we report two pairs of MR-TADF materials (Czp-tBuCzB, Czp-POAB) based on planar chiral paracyclophane with photoluminescence quantum yields of up to 98 %. The enantiomers showed symmetric circularly polarized photoluminescence spectra with dissymmetry factors |g_PL| of up to 1.6×10⁻³ in doped films. Meanwhile, the sky-blue CP-OLEDs with (R/S)-Czp-tBuCzB showed an external quantum efficiency of 32.1 % with the narrowest full-width at half-maximum of 24 nm among the reported CP-OLEDs, while the devices with (R/S)-Czp-POAB displayed the first nearly pure green CP electroluminescence with |g_EL| factors at the 10⁻³ level. These results demonstrate the incorporation of planar chirality into MR-TADF emitter is a reliable strategy for constructing of efficient CP-OLEDs.     

Conformationally Locked Cyclo[2]Dipyrrins Linked with Anthracene Subunits: Synthesis and Chiroptical Properties

Herein, we report the synthesis of anthracene-containing twisted cyclo[2]dipyrrin 1 by utilizing a non-planar building block, 1,5-dipyrrylanthracene (1,5-DPA). The non-planar nature of the macrocycle enhanced the solubility and helped in structural characterization. Macrocycle 1 adopts a twisted ‘figure of eight’ conformation stabilized by strong intramolecular H-bonding interactions and exists as a pair of helical enantiomers, as revealed by X-ray crystallographic analysis. More importantly, the sterically locked structure enabled facile optical resolution using chiral HPLC. The (P,P) and (M,M) enantiomers show moderate chiroptical properties, such as absorption dissymmetry factors |g_abs| in the order of 10⁻³, and luminescence dissymmetry factors |g_lum| of 3.8×10⁻³ and 2.9×10⁻³ at 702 nm, respectively.     

Precise Synthesis of Optically Active and Thermo-degradable Poly(trifluoromethyl methylene) with Circularly Polarized Luminescence

Developing high performance and environment-friendly fluoropolymers is greatly desired. In this work, we found that 2-diazo-1,1,1-trifluoroethane can be polymerized by air-stable alkyne-palladium(II) catalysts following a living polymerization mechanism, affording a fluoropolymer, poly(trifluoromethyl methylene) in high yield with controlled molar mass and low dispersity. This polymer bears trifluoromethyl on every main chain atom and thus has good resistance to chemical corrosion, high hydrophobicity, and excellent dielectric constant with low dielectric loss. Due to the steric hindrance between the trifluoromethyl pendants, the synthetic poly(trifluoromethyl methylene) can twist into a stable helix. The one-handed preferred helices synthesized using chiral Pd^II-catalysts exhibit high optical activity and circularly polarized luminescence. Remarkably, such polymer can be completely degraded to (E)-1,1,1,4,4,4-hexafluorobut-2-ene at high temperatures (>280 °C). Additionally, taking advantage of the living chain end, the polymer can be further modified.     

A Fused [5]Helicene Dimer with a Figure-Eight Topology: Synthesis,Chiral Resolution,and Electronic Properties

Chiral shape-persistent molecular nanocarbons are promising chiroptical materials; their synthesis, however, remains a big challenge. Herein, we report the facile synthesis and chiral resolution of a double-stranded figure-eight carbon nanobelt 1 in which two [5]helicene units are fused together. Two synthetic routes were developed, and, in particular, a strategy involving Suzuki coupling-mediated macrocyclization followed by Bi(OTf)₃-catalyzed cyclization of vinyl ether turned out to be the most efficient. The structure of 1 was confirmed by X-ray crystallographic analysis. The isolated (P,P)- and (M,M)- enantiomers show persistent chiroptical properties with relatively large dissymmetric factors (|g_abs|=5.4×10⁻³ and |g_lum|=1.0×10⁻²), which can be explained by the effective electron delocalization along the fully conjugated belt and the unique D₂ symmetry. 1 exhibits local aromatic character with a dominant structure containing eight Clar's aromatic sextet rings.