Search

Without stereogenic carbon centers, organic molecules can be chiral when they have large energy barriers for conformational inversion. In this work, conformational behaviors are investigated for a series of tricyclic propellane skeletons with increasing 6‐membered‐ring peripheral moieties fused with aromatic rings. According to theoretical calculations, trinaphtho[3.3.3]propellane has three vertical naphthalene rings like triptycene shape without torsion along the central C−C single bond. On the other hand, hexabenzo[4.4.4]propellane shows hexaphenylethane‐like ca. 60° twist along the bond with large activation energy of 64 kcal mol−1 for twist inversion because of the high congestion caused by three 6‐membered‐ring loops. Indeed, the [4.4.4]propellane gives a stable pair of chiroptical enantiomers toward heating at 146 °C. By contrast, a hybrid [4.3.3]propellane exhibits fast interconversion between two twisted conformations even at −80 °C. [ABSTRACT FROM AUTHOR]

Pillar[5]arene is a promising macrocyclic receptor of a chemical sensor showing shape-selective encapsulation of neutral molecules into the cavity, but the poor fluorescence properties remain a challenge. Herein, we report a pillar[5]arene coupled with 2-(2-hydroxyphenyl)benzoxazole (HBO), which displays bright fluorescence in both solution and the solid state. Owing to the excited-state intramolecular proton transfer (ESIPT) in the HBO moiety, greatly improved fluorescence is observed for the pillar[5]arene derivative in CHCl3 (Φ lum = 11%) and powder form (Φ lum = 25%). Moreover, the emission color changes from light green to blue when the powder sample is exposed to n -hexane vapor. The color change derives from variable dual emission via ESIPT and excimer-forming pathways, as suggested by fluorescence lifetime measurements at different wavelengths. Powder x-ray diffraction indicates that increased crystallinity and a small alteration in the solid-state structure leads to visible fluorescent chromism upon vapor encapsulation. [ABSTRACT FROM AUTHOR]

Single-atomic metal catalysts are attractive for green chemistry in terms of their outstanding catalytic performance and savings in precious metal usage owing to maximized metal utilization, including anode catalysts in polymer electrolyte fuel cells (PEFCs). Heteroatom-doped porous carbons are extensively used as supports, where the heteroatoms contribute to the immobilization of single-atomic metals. However, high-content doping of heteroatoms, especially sulphur (S), into carbon supports is still challenging because S species can be readily desorbed during heat treatment. Herein, we present a bottom-up fabrication approach for S-rich porous carbons from molecular precursors via a thermal polymerization process. A simple carbonization of molecules with thermally stable S-containing building blocks and polymerizable ethynyl moieties at 900 °C yields microporous carbon materials with record-high S content (over 15 wt%). The abundant S species function as an effective anchoring site for single-atomic platinum (Pt) species. Toward anode catalysts in PEFCs, the prepared single-atomic Pt catalysts efficiently promote the electrochemical hydrogen oxidation reaction, whose activity is comparable to that of commercial Pt/C, despite the significantly low Pt loading amount. [ABSTRACT FROM AUTHOR]

Macrocyclic arenes show conformational adaptability, which allows host–guest complexations with the size‐matched guest molecules. However, their emission properties are often poor in the solid states due to the self‐absorption. Herein, we newly synthesized pillar[6]arene derivatives having alternate methylene and nitrogen bridging structures. Solvatochromic study reveals that the nitrogen‐embedding into the cyclic structures can strengthen the intramolecular charge transfer (CT) nature compared to that of the linear nitrogen‐bridged precursor. Owing to the large Stokes shift in the solid state, one of the nitrogen‐embedded pillar[6]arenes shows high absolute photoluminescence quantum yield (ΦPL=0.36). Furthermore, it displays a turn‐off sensing ability toward nitrobenzene (NB) vapor; a fluorescence quenching is observed when exposed to the NB vapor. From the structural analysis before and after the exposure of NB vapor, the amorphous nitrogen‐embedded pillar[6]arene efficiently co‐crystallize with NB and formed non‐emissive intermolecular CT complexes with NB. [ABSTRACT FROM AUTHOR]

Solid‐state assembling modes are as crucial as the chemical structures of single molecules for real applications. In this work, solid‐state structures and phase‐transition temperatures are investigated for a series of fluoranthene‐fused [3.3.3]propellanes consisting of a rigid three‐dimensional (3D) π‐core and varying lengths of alkoxy groups. Compounds in this series with n‐butoxy or longer alkoxy groups take an amorphous state at room temperature. In these molecules, rotatable biaryl‐type bonds are not incorporated and high D3h molecular symmetry is retained. Therefore, π‐fused [3.3.3]propellanes present a unique platform for amorphous molecular materials with low ratios of flexible alkoxy atoms to rigid π‐core ones. [ABSTRACT FROM AUTHOR]

Fluorocarbon gases are regarded as one of the largest contributors to serious environmental problems such as ozone‐depletion and global warming, and thus, the development of reclamation technologies is in great demand for reducing emission of such harmful compounds. So far, porous materials such as zeolites, activated carbons, and metal‐organic frameworks (MOFs) have been examined as solid‐state absorbents for fluorocarbon gases. However, such porous materials often suffer from a lack of size‐selectivity in fluorocarbon gas uptakes due to the large‐sized cavities (>1 nm). Herein, it is reported that macrocyclic pillar[n]quinones (P[n]Q, n = 5 or 6) in crystalline state show size‐selective uptake for fluorocarbon gases owing to their molecular‐scale cavities (<1 nm). The P[n]Q also show uptake behaviors for volatile halogenated organic compounds (VHOCs), which are highly toxic. Interestingly, the volatilities of VHOCs within the 1D channels of P[5]Q are drastically reduced compared with those of the bulk VHOC solvents. Experimental results and computational analyses revealed that the excellent storage abilities of the crystalline P[n]Q are a synergic result of their electron‐deficient macrocyclic scaffolds and the basic carbonyl oxygen atoms on their rims. [ABSTRACT FROM AUTHOR]

Regioregular and random conjugated polymers based on a boron‐fused azomethine unit were synthesized by Sonogashira–Hagihara cross coupling reaction. Although these polymers exhibited similar optical properties in the solution states, a distinct difference was observed in the aggregation forming ability in the film states; scanning electron microscope (SEM) observation indicated the existence of fiber‐like aggregates in the spin‐coated film of the regioregular polymer, while regiorandom polymer showed no aggregate in the film state. Accordingly, the UV–vis absorption spectrum of the regioregular polymer showed an increased shoulder peak due to the aggregate formation, whereas the random one showed no change. Furthermore, an absolute fluorescence quantum efficiency of the regioregular polymer was enhanced in response to the aggregate disassembly via thermal annealing treatment. In this study, we demonstrate that controlling regioregularity of the conjugated polymers can induce the different morphological structures and thermal‐responsive behaviors. These findings could be beneficial for the design strategy and potential applications of thin‐film optoelectronic devices with stimuli‐responsive properties. [ABSTRACT FROM AUTHOR]

Pillar[n]arenes can be constructed using a Friedel–Crafts alkylation process. However, due to the reversible nature of the alkylation, mixture of large pillar[n]arenes (n≥7) are obtained as minor products, and thus laborious purification are necessary to isolate the larger pillar[n]arenes. Moreover, inert methylene bridges are introduced during the alkylation process, and the multi‐functionalization of the bridges has never been investigated. Herein, an irreversible Friedel–Crafts acylation is used to prepare pillar[n]arenes. Due to the irreversible nature of the acylation, the reaction of precursors bearing carboxylic acids and electron‐rich arene rings results in a size‐exclusive formation of pillar[n]arenes, in which the ring‐size is determined by the precursor length. Because of this size‐selective formation, laborious separation of undesired macrocycles is not necessary. Moreover, the bridges of pillar[n]arenes are selectively installed with reactive carbonyl groups using the acylation method, whose positions are determined by the precursor used. The carbonyl bridges can be easily converted into versatile functional groups, leading to various laterally modified pillar[n]arenes, which cannot be accessed by the alkylation strategy. [ABSTRACT FROM AUTHOR]

A three-dimensional skeleton, π-fused [4.3.3]propellane, was constructed and derivatized by selective π-extension at the two naphthalene units. The obtained propellanes existed as stereoisomers different in spatial arrangement, one of which displayed a chiroptical response originating from through-space interactions between 5-azachrysenes in a skew position. [ABSTRACT FROM AUTHOR]