三宅 由寛

Mimicking the interconvertible carbon allotropes of 2-dimensional (2D) graphene and 1-dimensional (1D) carbon nanotubes (CNTs), herein we report the in situ transformation of 2D π-conjugated covalent organic frameworks (COFs) sheet into 1D nanotubular structures via self-assembly the sheets at solvent interfaces. The facile “roll-sheets” self-assembly resulted in coaxial nanotubes with uniform cross-sectional diameter, which was realized for diazapyrene-based COFs but not for the corresponding pyrene COF, although both possess similar chemical structures. Upon replacing the carbon atoms at 2,7-positions of pyrene with nitrogen, contrasting optical and electronic properties were realized, reflecting the rolled structure of the conjugated 2D sheets. The nanotubes exhibited concerted electronic- and proton-conducting nature with stable conducting pathways at ambient conditions. The nitrogen centers act simultaneously as the site for charge carrier doping and proton acceptors, as evidenced by the high photo- and electrical conductivity, as well as the record proton conductivity (σ = 1.98 S cm ⁻¹ ) results. The present diazapyrene-based 1D nanotubular COF serves as a unique materials platform with electronic conduction in the wall and proton conduction in the core, respectively.

We prepared a free-base 10,20-diphenyl-5,15-diazaporphyrin and its Ni(II), Cu(II), Pd(II), and Pt(II) complexes. These molecules uniformly form an infinite one-dimensional [Formula: see text]-stacking array in the solid state. The four-fold intermolecular hydrogen bonding interactions between the meso-nitrogen atom of the diazaporphyrin core and the ortho-hydrogen atom of the phenyl substituent dominate the crystal packing arrangement. The present study revealed that the meso-nitrogen atom of diazaporphyrins would be used as an inherent hydrogen bonding acceptor to construct supramolecular assemblies.

Abstract We have succeeded in the synthesis of various tetrasilatetrathia[8]circulenes with alkyl and aryl groups on the silicon atoms. We also disclosed the effect of phosphine ligands on palladium-catalyzed silylation of tetraiodotetrathienylene and rhodium-catalyzed intramolecular silylation of tetrasilyltetrathienylenes. Experimental and theoretical analysis revealed the effect of the substituents on the silicon atoms on their electronic property.

<jats:p> Fluorination of sp<jats:sup>3</jats:sup> C–H bonds has attracted considerable attention as a promising method for the synthesis of organofluorine compounds. Manganese porphyrins have been extensively investigated as catalysts in the fluorination of saturated sp<jats:sup>3</jats:sup> C–H bonds. Recently, we have found that iron(III) 5,15-diazaporphyrins, which are porphyrin analogues with imine-type sp<jats:sup>2</jats:sup>-hybridized nitrogen atoms at the meso-positions, showed high catalytic performance in the oxidation of sp<jats:sup>3</jats:sup> C–H bonds. Here we disclose the synthesis, structure, and electronic properties of manganese(III) 5,15-diazaporphyrins. We also demonstrate the catalysis of chloromanganese(III) 5,15-diazaporphyrins for benzylic fluorination. </jats:p>

<p>Iron hexamesityl-5,15-diazaporphyrin was successfully synthesized. Its use for catalytic oxidation of cyclooctane showed high performance with a total TON up to 731. The introduction of bulky mesityl groups prevented the catalyst deactivation via formation of a μ-oxo dimer.</p>

5,15-Diazaporphyrins are porphyrin analogues with imine-type sp2-hybridized nitrogen atoms at the meso-positions. Even though these compounds are more electron-deficient than regular porphyrins, the use of iron diazaporphyrins as catalysts has not been reported. Herein, we disclose the synthesis, structure, and electronic properties of iron(III) 5,15-diazaporphyrins. We evaluate their structures and electronic natures by X-ray analysis and electrochemical analyses. We also demonstrate that chloroiron(III) 5,15-diazaporphyrins exhibit high catalytic activity in the direct oxidation of alkanes due to their intrinsic electron-deficient nature. On the basis of stoichiometric reactions of iron(III) diazaporphyrin with iodosylbenzene as an oxidant, it was possible to demonstrate the existence of an iodosylbenzene-iron diazaporphyrin adduct reaction intermediate that serves as a reservoir to generate oxo-iron species.

<p>Synthetic route for hetero[8]circulenes are classified into the annulative construction of eight-membered ring and the peripheral ring fusion of eight-membered ring. Post-transformation enables the tuning of structural features and electronic nature.</p>