ABSTRACT
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.
ABSTRACT
Stimuli-responsive organic luminescent crystals have attracted significant attention in recent years for their potential in sensor and memory applications. While turn-on luminescence is superior in detection sensitivity compared with turn-off luminescence, the development of organic crystals that exhibit turn-on luminescence in response to multiple stimuli remains a significant challenge. Herein, the crystals of chiral bisimidazolyl 1,1'-bi-2-naphthol (BINOL) dimethyl ether have exhibited a dual-stimuli-responsive turn-on luminescence based on two distinct mechanisms. In the crystalline state, luminescence was substantially quenched by the intermolecular hydrogen bonds between the imidazole rings. Mechanical stimulation induced a transition to a blue-violet-emissive amorphous state. In contrast, thermal stimulation produced an orange luminescence, attributed to excited-state intramolecular proton transfer (ESIPT) luminescence from thermally demethylated products. Furthermore, the thermally induced state exhibited circularly polarized luminescence (CPL), marking a rare instance of stimuli-responsive turn-on CPL in a solid-state system. This study provides new insights into environmental and structural factors for solid-state luminescent properties and advances the design guidelines for multifunctional luminescent sensors.
ABSTRACT
5,5',6,6',7,7',8,8'-Octahydro-1,1'-bi-2-naphthol (hbNaph) is an axially chiral molecule consisting of a smaller π-electronic system than that for 1,1'-bi-2-naphthol (BINOL). The absorption and circular dichroism (CD) bands of hbNaph appear in a shorter wavelength region below 310 nm, compared to those of BINOL, and its fluorescence is in the invisible UV region. However, increasing the concentration of hbNaph in solution up to 0.1 M results in its absorption edge gradually extending to longer wavelength, with a shoulder around 330 nm, and finally increasing to about 450 nm. At the same time, blue fluorescence is clearly observed, as well as a new CD band with the sign of the Cotton signals reversed from those obtained for dilute solutions. These results suggest that, at high concentrations, hbNaph forms chiral aggregates, in which π-electrons are delocalized over multiple molecules. To further understand how molecular axial chirality is transformed to supramolecular chirality, we attempted to construct aggregate models by simulating CD spectra using a time-dependent density functional theory. The only reasonable model obtained was that involving the counterclockwise R-enantiomer forming a clockwise helix, while the clockwise S-enantiomer forms a counterclockwise helix. We conclude, however, that, for such helixes, the most plausible model is densely packed and forms when the dihedral angle between the two phenol rings of hbNaph is acute, at around 75°, which reproduces the aggregate-induced CD sign inversion.
ABSTRACT
A chiral platinum(II) complex with a helical Schiff-base [4]helicene ligand exhibits intense red circularly polarized phosphorescence (CPP) with a glum of 0.010 in the dilute solution state. The intense CPP was caused by a change in the electronic transition character based on the induction of the helical structure.
ABSTRACT
Boron complexes with Schiff-base [4]helicene ligands were synthesized. These complexes were characterized by NMR spectroscopy and their helical molecular structures were unequivocally established by X-ray diffraction (XRD) analysis. The helical boron complexes exhibited efficient photoluminescence under UV irradiation, and the circularly polarized luminescence (CPL) properties were investigated for optically pure samples. Density functional theory (DFT) calculations were conducted to further understand their photophysical properties including chiroptical responses.
ABSTRACT
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.
Subject(s)
Luminescence , Polycyclic Compounds , HumansABSTRACT
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.
