Language：English   Publisher：Angewandte Chemie - International Edition  

We report the unprecedented sergeants and soldiers (S&S)-type remote control of one-handed helicity in copolymers of chiral/achiral biphenylylacetylenes bearing amphiphilic oligo(ethylene glycol) (OEG) side chains. A small amount of chiral binaphthyl residues (≤10 mol %) introduced at the terminal of the achiral OEG spacers as many as 80 bonds away from the polymer backbones induced a complete one-handed helix in water through preferential intramolecular encapsulation of the binaphthyl groups within a cavity of the copolymers. A fully one-handed helix can be induced virtually independent of the OEG spacer length and concentrations. At a specific spacer length, however, its helix-sense was inverted. The copolymers also form an excess one-handed helix in organic solvents in an OEG spacer-length dependent manner, yet far from the polymer backbones. We show the superiority of the present covalent-bond driven S&S-type remote helicity control over the corresponding noncovalent helicity induction approach.

DOI： 10.1002/anie.202301127

Web of Science

Scopus

PubMed

Language：English   Publisher：Angewandte Chemie - International Edition  

Enantiopure [6]helicene containing an embedded seven-membered ring and carbo[7]helicene (>99 % ee) with opposite helicity were simultaneously and quantitatively (>99 %) synthesized with a perfect stereospecificity through stepwise acid-promoted intramolecular alkyne annulations of doubly axial-chiral cyclization precursors. The helical handedness of the [6]- and [7]helicenes was fully stereocontrolled by the doubly axial chirality of the precursors as a result of complete axial-to-helical chirality transfer. The cyclizations proceeded in a stepwise manner; the first six-membered ring formation was followed by the kinetically controlled seven- or six-membered ring formation with or without helix-inversion of a [4]helicene intermediate generated during the first cyclization step, thus quantitatively producing enantiopure circularly polarized luminescent [6]- and [7]helicenes with opposite helicity.

DOI： 10.1002/anie.202301836

Web of Science

Scopus

PubMed

Language：English   Publisher：Angewandte Chemie - International Edition  

Defect-free one-handed contracted helical tubular ladder polymers with a π-electron-rich cylindrical helical cavity were synthesized by alkyne benzannulations of the random-coil precursor polymers containing 6,6′-linked-1,1′-spirobiindane-7,7′-diol-based chiral monomer units. The resulting tightly-twisted helical tubular ladder polymers showed remarkably high enantioseparation abilities toward a variety of chiral hydrophobic aromatics with point, axial, and planar chiralities. The random-coil precursor polymer and analogous rigid-rod extended helical ribbon-like ladder polymer with no internal helical cavity exhibited no resolution abilities. The molecular dynamics simulations suggested that the π-electron-rich cylindrical helical cavity formed in the tightly-twisted tubular helical ladder structures is of key importance for producing the highly-enantioseparation ability, by which chiral aromatics can be enantioselectively encapsulated by specific π-π and/or hydrophobic interactions.

DOI： 10.1002/anie.202218297

Web of Science

Scopus

PubMed

Publishing type：Research paper (scientific journal)   Publisher：World Scientific Pub Co Pte Ltd  

DOI： 10.1142/S1088424622500869

Web of Science

Scopus

researchmap

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry (RSC)  

Tropo(thio)ne-embedded homoHPHACs and their dications were synthesised by an electrophilic annulation of secoHPHAC and successive oxidation. 13C NMR spectra of the dications represented global 22π homoaromaticity via homoconjugation, while alkylation...

DOI： 10.1039/d1cc07152a

Web of Science

Scopus

PubMed

researchmap

Language：English   Publishing type：Research paper (scientific journal)  

A rigid wing-shaped bicyclo[2.2.2]octadiene-fused bis-hexapyrrolohexaazacoronene (HPHAC) is synthesized, and subsequent chemical oxidation affords a stable biradical dication and an aromatic tetracation. The physicochemical properties and single-crystal structures in various oxidation states are characterized. The face-to-face π-stacked dimeric structures are observed in the neutral and dicationic states. The HPHAC flakes can act as aromatic walls in a tetracation state, producing enlarged induced magnetic shielding space through the superimposition effect.

DOI： 10.1021/acs.orglett.1c03669

Web of Science

Scopus

PubMed

researchmap

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A hexapyrrolohexaazacoronene (HPHAC) with 12 less-bulky peripheral ethyl groups than its aryl-containing HPHAC counterpart was synthesized to investigate the innate character of HPHAC. X-ray diffraction analysis revealed that HPHAC had a planar structure and close packing because of CH-p interactions between the alkyl groups and the HPHAC core. Compared to the previously reported HPHAC decorated with 12 peripheral aryl groups, this electron-rich p-system exhibited reversible multistep oxidations at low potentials and easily formed mono- and dicationic salts and charge-transfer (CT) complexes with 7,7,8,8-tetracyano-p-quinodimethane. These oxidized species exhibited clear changes in the bond-length alternation of the pyrrole units in the crystal state, indicating charge and spin delocalization. The distinct upfield shift of the central carbon signal of the dication in the C-13 NMR spectrum affirms the global aromaticity from the viewpoint of a magnetic criterion. In the UV-vis/NIR spectra, broad absorption in the NIR region was observed only for HPHAC(2+) and not the structurally similar cyclo[6]pyrrole. Magnetic circular dichroism measurements and time-dependent density functional theory calculations revealed that the broad absorption was assigned to the CT transition from the central benzene ring to the outer pyrrole rings.

DOI： 10.1021/acs.joc.0c03042

Web of Science

Scopus

PubMed

researchmap

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

An antiaromatic cation of the expanded hexapyrrolohexaazacoronene (HPHAC) 1(+) was synthesized by a Vilsmeier-type reaction of the partially unfused HPHAC 2. X-ray diffraction analysis revealed the formation of a seven-membered ring with a methyne linkage between the pyrrole moieties. Although 1(+) is a monocation, upfield shifts of the peripheral ethyl protons were clearly observed in the H-1 NMR spectra, indicating 24 pi antiaromaticity. Global antiaromaticity was also supported by nucleus-independent chemical shift and anisotropy of the induced current density calculations. Cation 1(+) displayed two reversible oxidations and one irreversible reduction in the cyclic voltammetry measurements. Treatment of 1(+) with NOSbF6 gave aromatic trication 1(3+) with 22 pi-electron conjugation.

DOI： 10.1021/jacs.9b09260

Web of Science

Scopus

PubMed

researchmap

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A core-expanded, pyrrole-fused azacoronene analogue containing two unusual N-doped heptagons was obtained from commercially available octafluoronaphthalene and 3,4-diethylpyrrole in two steps as a heteroatom-doped nonplanar nanographene. Full fusion with the formation of the tetraazadipleiadiene framework and the longitudinally twisted structure was unambiguously confirmed by single-crystal X-ray diffraction analysis. The edge-to-edge dihedral angle along the acene moiety was 63 degrees. This electron-rich pi-system showed four reversible oxidation peaks. Despite the nonplanar structure, the Huckel aromaticity owing to a peripheral pi-conjugation in the dicationic state was concluded from the bond-length alternation and nucleus-independent chemical shift (NICS) and anisotropy of the induced current density (ACID) calculations.

DOI： 10.1021/jacs.8b06079

Web of Science

Scopus

PubMed

researchmap

Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

A cyclophane composed of diethanoanthracene (DEA)-fused dipyrrole and tetrafluorobenzene was synthesized by one-pot aromatic nucleophilic substitution (SNAr). Reflecting the fixed angle of DEA-fused dipyrrole, X-ray single-crystal structure analysis of the cyclophane revealed its rice-ball-shaped structure.

DOI： 10.1246/cl.161026

Web of Science

Scopus

CiNii Research

researchmap