Chiroptically Active Host-Guest Composites Using a Terpene-Based Micellar Capsule.

For the design of a new chiroptically active host-guest system, a bent amphiphilic compound was synthesized using cyclic monoterpenes as key biorelated chiral frameworks. In water, the bent amphiphiles form a terpene-based micellar capsule with a core diameter of ∼2 nm in a spontaneous and quantitative fashion. The resultant chiral capsule shows wide-ranging uptake abilities toward achiral fluorescent dyes in water. Notably, relatively strong CD bands are generated from the resultant host-guest composites, e.g., possessing AIE-active tetraphenylethene and sterically demanding BODIPY dyes, through efficient host-to-guest chirality transfer. The composites also display CPL, with moderate to high emission asymmetry factors (|glum| = up to 3.3 × 10-3).

Synthesis and Isolation of a Homochiral Nanohoop Composed of a Tröger's Base and Hexaparaphenylene.

Invited for the cover of this issue are Yusuke Yoshigoe, Hirotaka Shimada, and Shinichi Saito at the Tokyo University of Science, and Takuya Takaki and Yoshitane Imai at Kindai University. The image depicts a witch with a racemic pair of our nanohoops, TB[6]CPPs, chanting words shown in the font of a magical world. Read the full text of the article at 10.1002/chem.202304059.

Synthesis and Isolation of a Homochiral Nanohoop Composed of a Tröger's Base and Hexaparaphenylene.

The synthesis of a new nanohoop containing a stereogenic Tröger's base skeleton tethered to a curved hexaparaphenylene ([6]CPP) is reported. The TB[6]CPP nanohoop possesses a stable C2 symmetrical structure, which promotes the allowed transition that gives rise to pale blue emission with a quantum yield of ~0.69, surpassing the value of the more symmetrical [8]CPP. Moreover, TB[6]CPP shows chiroptical properties including circular dichroism and circularly polarized luminescence with a moderate dissymmetry factor (|glum|) of ~2.1×10-3.

Configuration of two cysteine residues in a ring within a stapled Bim peptide affects the secondary structure and apoptotic activity.

Many reports have shown that stabilization of secondary structure by stapling functional peptides enhances the intracellular bioactivity. However, no report has discussed the correlation between stabilization and biological activity based on the configuration of amino acid residues used as anchors for stapling. To clarify this, we investigated the helix content and apoptotic efficiency of an apoptosis-inducing peptide, Bim, and four stapled Bim peptides containing stapling-related Cys residues introduced with different configurations within the sequence. The results demonstrated that the configuration of Cys residues in stapled Bim peptides affected the secondary structure and intracellular activity of the peptides, and furthermore, there was a correlation between these latter two variables.

Circularly polarised luminescence from intramolecular excimer emission of bis-1,8-naphthalimide derivatives.

Chiral excimers exhibit unique photophysical behaviour. However, further molecular design is required along with systematic studies on the effect of spacer groups and solvent polarity. In this study, we prepared four circularly polarised luminescence (CPL)-active molecules that exhibit intramolecular excimer emission. Bis-1,8-naphthalimide (bNI) derivatives D-LybNI, L-LybNI, D-LyMebNI, and L-LyMebNI were prepared with chiral backbones and alkyl linkages between the NI rings with chain lengths of five carbon atoms, suitable for excimer fluorescence. The fluorescence properties were investigated experimentally and theoretically using density functional theory. The molecules exhibited intramolecular excimer fluorescence in polar organic solvents. Mirror-image circular dichroism and CPL spectra were obtained for the D and L forms. D- and L-LyMebNI exhibited relatively large luminescence dissymmetry factors (|glum|) in acetonitrile of 1.9 × 10-3 and 1.6 × 10-3, respectively. Thus, this study demonstrates chiral bNI derivatives with simple synthesis procedures that emit intramolecular excimer fluorescence and have effective CPL properties. These molecules are promising for developing organic molecular systems with bright, highly polarised emission.

Impact of helical elongation of symmetric oxa[n]helicenes on their structural, photophysical, and chiroptical characteristics.

The adjustment of the main helical scaffold in helicenes is a fundamental strategy for modulating their optical features, thereby enhancing their potential for diverse applications. This work explores the influence of helical elongation (n = 5-9) on the structural, photophysical, and chiroptical features of symmetric oxa[n]helicenes. Crystal structure analyses revealed structural variations with helical extension, impacting torsion angles, helical pitch, and packing arrangements. Through theoretical investigations using density functional theory (DFT) calculations, the impact of helical extension on aromaticity, planarity distortion, and heightened chiral stability were discussed. Photophysical features were studied through spectrophotometric analysis, with insights gained through time-dependent DFT (TD-DFT) calculations. Following optical resolution via chiral high-performance liquid chromatography (HPLC), the chiroptical properties of both enantiomers of oxa[7]helicene and oxa[9]helicene were investigated. A slight variation in the main helical scaffold of oxa[n]helicenes from [7] to [9] induced an approximately three-fold increase in dissymmetry factors with the biggest values of|glum| of oxa[9]helicene (2.2 × 10-3) compared to|glum|of oxa[7]helicene (0.8 × 10-3), findings discussed and supported by TD-DFT calculations.

Construction of high-throughput magnetic circular dichroism measurement system and its application to research on magnetic and optical properties of phthalocyanine complexes.

Magnetic circular dichroism (MCD) spectroscopy is a powerful method for evaluating the electronic structure and magnetic and optical properties of molecules. In particular, MCD measurements have been performed on phthalocyanines and porphyrins with various central metal ions, axial ligands, and substituents to elucidate their properties. It is essential to develop a robust high-throughput technique to perform these measurements comprehensively and efficiently. However, MCD spectroscopy requires very high optical quality for each component of the instrument, and even slight cell distortions can impair the baseline flatness. Consequently, when versatility and data quality are important, an optical system designed for a microplate reader is not suitable for the MCD spectrometer. Therefore, in this study, we develop a new magnetic flow-through cell and combine it with an existing CD spectrometer and autosampler to construct a high-throughput system. The effectiveness and performance of this new system are then evaluated. In addition, based on the MCD and absorption spectra of various phthalocyanine complexes, the effects of substituents and solvents on their magnetic and optical properties and the causes of these effects are discussed. The results demonstrate that this system is effective for the evaluation of the physicochemical properties of various phthalocyanine complexes.

Single Molecular Persistent Room-Temperature Phosphorescence and Circularly Polarized Luminescence from Binaphthol-Decorated Optically Innocent Cyclotriphosphazenes.

Circularly polarized luminescence (CPL) features of BINOL-decorated cyclotriphosphazenes (CPs) are reported for the first time. The luminescence dissymmetry factor (glum ) of these compounds in chloroform solutions and polymethyl methacrylate (PMMA) thin films with wt 1 % doping concentrations are found to be 1.0×10-3 , and 2.9×10-3 , respectively. However, no CPL signal is observed for the pristine solids. The enantiomers (CP-(R)/CP-(S)) show ultraviolet photoluminescence (~350-360 nm) in solution and the solid state. These compounds show ~10 times larger absolute photoluminescence quantum yield (PLQY) than the simple BINOLs in the solutions state. In the solid state, CP-(R) shows larger PLQY than binaphthol-(R); in contrast, the S enantiomer shows lower PLQY than binaphthol-(S); this indicates that the isomer-dependent solid-state packing of these compounds plays a crucial role in controlling the PL. Thin films with more than 1 % doping concentration and pristine solids of these compounds do not show persistent room-temperature phosphorescence (pRTP) due to concentration-caused quenching. However, thin films with wt 1 % of these chiral emitters exhibit pRTP characteristics with a ~159-343 ms lifetime under vacuum. Theoretical calculations reveal that the cyclophosphazene acts as an optically innocent dendritic core, and the optical features of these compounds are dictated by the pendent BINOL chromophore.

Chiroptical Response Control of Planar and Axially Chiral Polymethylene-Vaulted Platinum(II) Complexes Bearing 1,1'-Binaphthyl Frameworks.

In this study, the synthesis, structure, and chiroptical response control of planar chiral polymethylene-vaulted trans-bis[(ß-iminomethyl)aryloxy]platinum(II) complexes bearing axially chiral 1,1'-binaphthyl ligands are described. A series of enantiopure polymethylene (n = 4-10)-vaulted complexes were prepared in 6 steps using commercially available (R)- or (S)-BINOL as the starting material without an optical resolution process. The trans-coordination and three-dimensional vaulted structures of the platinum complexes were elucidated from X-ray diffraction (XRD) studies. The complexes were found to show structural dependence of chiroptical responses in the dilute solution state such that the absolute values of [α]D, dissymmetry factors gabs in circular dichroism (CD), and glum in circularly polarized luminescence (CPL) increased upon shortening the length of the polymethylene bridges. The enhanced chiroptical responses were theoretically investigated using density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, and the results are discussed in terms of the molecular structures and transition dipole moments of the ground states. The structural dependence of the chiroptical responses was ascribed to the distortion of the coordination platforms caused by restriction of the vaulting methylene linkers.

Charge-Segregated Stacking Structure with Anisotropic Electric Conductivity in NIR-Absorbing and Emitting Positively Charged π-Electronic Systems.

Squarylium-based π-electronic cation with an augmented dipole was synthesized by methylation of zwitterionic squarylium. The cation formed various ion pairs in combination with anions, and the ion pairs exhibited distinct photophysical properties in the dispersed state, ascribed to the formation of J- and H-aggregates. The ion pairs provided solid-state assemblies based on cation stacking. It is noteworthy that complete segregation of cations and anions was observed in a pseudo-polymorph of the ion pair with pentacyanocyclopentadienide as a π-electronic anion. In the crystalline state, the ion pairs exhibited photophysical properties and electric conductivity derived from cation stacking. In particular, the charge-segregated ion-pairing assembly induces an electric conductive pathway along the stacking axis. The charge-segregated mode and fascinating properties were derived from the reduced electrostatic repulsion between adjacent π-electronic cations via dipole-dipole interactions.

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 (|glum |=(1.3-1.9)×10-3 ) that can be attributed to structural changes in the interior of the helicene helix.

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

Invited for the cover of this issue are the groups of Kazuteru Usui and Satoru Karasawa at Showa Pharmaceutical University, and Yoshitane Imai at Kindai University. The image depicts how a phosphine-oxide-bearing helicene exhibits markedly enhanced CPL response in the excited state compared with that of one with a corresponding phosphine. Read the full text of the article at 10.1002/chem.202202922.

Fluorescence ratiometric DNA detection by peptide nucleic acid-pyrene binary probes.

We developed a method for detecting DNA by excimer fluorescence from two peptide nucleic acids (PNAs) modified with a pyrene (Pyr). The two PNA-Pyr probes were prepared by solid-phase peptide synthesis, and we assessed fluorescence from the mixture of probes with DNA. From the results, excimer fluorescence derived from the two PNA-Pyr probes forming hybrids with the complementary DNA was observed, and the two probes showed the maximum excimer/monomer ratio when the probes and DNA were hybridized at a 1:1:1 ratio, indicating that the PNA-Pyr probes can detect target DNA. Furthermore, we adjusted the spatial arrangement between the two PNA-Pyr hybrids formed on the DNA to promote optimal excimer formation. As a result, optimal excimer formation was achieved by spacing the two nucleobases between the formed two hybrids and further inserting a hexamethylene linker (C6) between the PNA and Pyr of the PNA-Pyr probe on one side.

Multi-colour circularly polarized luminescence properties of chiral Schiff-base boron difluoride complexes.

A series of chiral Schiff-base boron difluoride complexes was synthesized and their photophysical properties were examined. These complexes showed multi-colour (blue, yellow and red) photoluminescence in solution and in the solid state with good emission quantum yield (Φ) depending on the π-systems of the ligands. The chiral complexes exhibited circularly polarized luminescence (CPL) with an absolute luminescence dissymmetry factor (glum) of up to the 1.3 × 10-3 in solution and 1.9 × 10-2 in the drop-cast film state. Density functional theory (DFT) and time-dependent (TD) DFT calculations were conducted to further understand the photophysical properties.

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

Invited for the cover of this issue are Masashi Hasegawa, Yoshitane Imai and co-workers at Kitasato University and Kindai University. The image depicts the reported figure-eight molecule as an M. C. Escher-inspired 'impossible object'. Read the full text of the article at 10.1002/chem.202005320.

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 )n O- 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 glum value (1.0-1.6×10-2 ) in circularly polarized luminescence (CPL) and unusual glum /gabs ratios (0.93-1.3). These experimental high |glum | 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 glum values.

Circularly Polarized Luminescence of a Stereogenic Curved Paraphenylene Anchoring a Chiral Binaphthyl in Solution and Solid State.

A curved stereogenic [6]paraphenylene ([6]PP), anchoring a chiral binaphthyl scaffold at 7,7'-positions, was prepared and investigated for its properties as a solid-state circularly polarized luminescence (CPL) dye. X-ray analysis revealed a helically twisted structure of PP units induced by axial chirality of binaphthyl framework. The curved [6]PP exhibits fluorescence in powder and polymethyl methacrylate (PMMA) film as well as solution. A significant increase in quantum yield was observed for a non-fluid PMMA film owing the suppression of the molecular motion. The gCPL values of the dye in solution and as PMMA film were almost the same (4.3-4.4×10-3 ) and lager than that in powder. TD-DFT calculations in the excited state suggest that the exciton can be delocalized into a twisted PP unit to produce a larger magnetic transition dipole moment.

Circularly Polarized Luminescence of a Stereogenic Curved Paraphenylene Anchoring a Chiral Binaphthyl in Solution and Solid State.

Invited for the cover of this issue are Masashi Hasegawa, Yoshitane Imai, Yasuhiro Mazaki and co-workers at Kitasato University, Kindai University and Osaka University. The image depicts a stereogenic twisted cycloparaphenylene that exhibits circularly polarized luminescence in a polymethyl methacrylate thin film. Read the full text of the article at 10.1002/chem.202004283.

Helical Oligophenylene Linked with [2.2]Paracyclophane: Stereogenic π-Conjugated Dye for Highly Emissive Chiroptical Properties.

A stereogenic π-system based on dimer (2) and trimer (3) of [2.2]paracyclophane (PC) and biphenyl was prepared and its structural, photophysical, and chiroptical properties were investigated. X-ray analysis revealed that the quaterphenyl moieties in 2 adopt a double helical structure anchoring [2.2]PC from both sides. Furthermore, 3 forms a isosceles triangle structure with a large chiral cavity. A homodesmotic reaction using DFT calculations revealed that 2 has a larger strain energy than 3 owing to its highly twisted phenylene linkers. Electronic and circular dichroic (CD) spectra were recorded in CH2 Cl2 solution. The spectra of both 2 and 3 are similar, and their longest absorption band accompanying a remarkable Cotton effect is attributed to the transition from HOMO to LUMO, which is delocalized to the quaterphenyl moiety. These compounds exhibit fairly high fluorescence quantum yields (ϕ=0.70-0.83) and moderate dissymmetry factor (|gCPL |=1.6×10-3 ) in circularly polarized luminescence (CPL).

Remarkable Effects of External Magnetic Field on Circularly Polarized Luminescence of EuIII (hfa)3 with Phosphine Chirality.

Herein, magnetic circularly polarized luminescence (CPL) (MCPL) spectroscopy was conducted to analyze an EuIII (hfa)3 complex with three chiral PIII -ligands. Resultantly, (R)-chirality luminophores with S-up orientation and (S)-chirality luminophores with N-up orientation were observed to possess symmetrical mirror image spectra, i. e., they were enantiomers. Similarly, the (R)-chirality luminophores with N-up orientation and the (S)-chirality luminophores with S-up orientation were also enantiomers. Contrarily, (R)-S-up and (S)-S-up were diastereomers and did not possess a mirror-image relationship. Likewise, (R)-N-up and (S)-N-up were diastereomers. The J-dependency of gMCPL and gCPL datasets suggested that the N-up/S-up external magnetic field, with the aid of chiral PIII -ligands, increased the gMCPL values by two- to sixteen-fold and modulated the gMCPL signs at J=1-4. Additionally, the origins of the nonideal mirror-symmetric CPL and MCPL spectral characteristics of EuIII (hfa)3 with three chiral PIII -ligands were discussed in terms of parity (space-inversion, P)-symmetry, time-reversal (T)-symmetry, and PT-symmetry laws.