記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Nature Communications  

Nanoporous solids, including metal-organic frameworks (MOFs), have long been known to capture small molecules by adsorption on their pore surfaces. Liquids are also known to accommodate small molecules by dissolution. These two processes have been recognized as fundamentally distinct phenomena because of the different nature of the medium—solids and liquids. Here, we report a dissolution-like gas accommodation so-called “adsorptive-dissolution” behavior in a MOF (PFAC-2) with pores densely filled with perfluoroalkyl chains. PFAC-2 does not have solvent-accessible voids; nevertheless, it captures oxygen molecules without changing the framework structure, analogous to molecular dissolution into liquids. Moreover, we demonstrate the selective capture of O<inf>2</inf> by PFAC-2 in a mixture of O<inf>2</inf> and Ar, which are difficult to separate due to their similarities such as boiling point and molecular size. Our results show the integration of molecular adsorption into nanospaces and dissolution into fluorous solvents, which can guide the design of crystalline adsorbents for selective molecular trapping and gas separation.

DOI： 10.1038/s41467-024-54391-y

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.4c06775

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.chempr.2024.06.033

記述言語：英語   掲載種別：研究論文（学術雑誌）  

<jats:title>Abstract</jats:title><jats:p>Conventional topochemical photopolymerization reactions occur exclusively in precisely-engineered photoactive crystalline states, which often produces high-insoluble polymers. To mitigate this, here, we report the mechanoactivation of photostable styryldipyrylium-based monomers, which results in their amorphization-enabled solid-state photopolymerization and produces soluble and processable amorphous polymers. A combination of solid-state nuclear magnetic resonance, X-ray diffraction, and absorption/fluorescence spectroscopy reveals the crucial role of a mechanically-disordered monomer phase in yielding polymers via photo-induced [2 + 2] cycloaddition reaction. Hence, mechanoactivation and amorphization can expand the scope of topochemical polymerization conditions to open up opportunities for generating polymers that are otherwise difficult to synthesize and analyze.</jats:p>

DOI： 10.1038/s43246-024-00539-8

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acsmaterialsau.3c00069

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Elsevier {BV}  

DOI： 10.1016/j.chempr.2023.06.007

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Elsevier {BV}  

DOI： 10.1016/j.trechm.2022.12.010

記述言語：英語   掲載種別：研究論文（学術雑誌）  

<jats:p>Visible-light-absorbing photoswitches based on the Azo-BF<jats:sub>2</jats:sub> scaffold show reversible isomerization in the solid state, storing photon energy and releasing thermal energy on demand.</jats:p>

DOI： 10.1039/d3sc03465h

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry A European Journal  

A thiophene-fused 1,4-diazapentalene (TAP) was rationally designed and synthesized as a C=N-containing 4n π-electron system that exhibits restored antiaromaticity impaired by the doping with C=N bonds. X-ray crystallographic analysis and quantum chemical calculations revealed that the annulation of thiophene rings with the 1,4-diazapentalene moiety resulted in a much higher antiaromaticity than the pristine 1,4-diazapentalene. These effects can be ascribed to the reduced bond alternation of the eight-membered-ring periphery caused by stabilization of the less-stable bond-shifted resonance structure upon increasing the degree of substitution of imine moieties. Consequently, TAP underwent facile hydrogenation even under mild conditions because of its pronounced antiaromaticity and the high aromaticity of the corresponding hydrogenated product H<inf>2</inf>-TAP. In addition, the electrophilic C=N moieties in TAP led to the formation of a dense π-stacked structure. These results highlight the effect of partial replacement of C=C bonds with C=N bonds in antiaromatic π-electron systems.

DOI： 10.1002/chem.202103122

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry A European Journal  

Invited for the cover of this issue are Aiko Fukazawa and co-workers at Kyoto University and Nagoya University. The image depicts the π-electrons as people to highlight the effect of fused aromatic rings in the antiaromatic π-electron systems. Read the full text of the article at 10.1002/chem.202004244.

DOI： 10.1002/chem.202004897

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Communications  

Seminaphtho-phospha-fluorescein (SNAPF), a phosphine-oxide-containing unsymmetric fluorescein dye, was synthesized based on the consecutive arylation of PhPCl<inf>2</inf>, followed by Friedel-Crafts cyclization. The resulting SNAPF exhibited several attractive photophysical properties including an intense fluorescence in the NIR region and a large Stokes shift.

DOI： 10.1039/c7cc04323f

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