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Synthesis in Nanospaces

Living systems achieve both near-perfect structural control and yield in the synthesis of biological macromolecules, such as DNA, RNA, and proteins. The key to this lies in the precisely shaped spaces within the enzymes where such chemical syntheses occur. Inspired by the biological systems, we are working extensively on developing the synthesis of novel nanomaterials by using artificial nanospace materials as templates. In 2005, our group achieved polymerization within the nanochannels of MOFs for the first time. Following this, MOFs have come to be recognized as a promising nanoreactor platforms for polymerization. Taking advantage of various nanospace materials, now including COFs and organic cages, we have developed innovative and unprecedented polymerization systems, attaining functional polymers otherwise inaccessible by conventional methods. As this method can be applied to many materials, such as biopolymers, inorganic nanomaterials, and nanocarbons, it is expected to produce a new academic trend in a wide range of research fields and have a significant impact on industry.

Precise synthesis of polymers enabled by nanospaces



Radical polymerisation of styrene in porous coordination polymers 
Chem. Commun. 2005, 5968–5970.

Functionalization of Coordination Nanochannels for Controlling Tacticity in Radical Vinyl Polymerization
J. Am. Chem. Soc. 2010, 132, 4917-4924.

Radical Polymerization of Vinyl Monomers in Porous Organic Cages
Angew. Chem. Int. Ed. 2016, 55, 6443-6447.

Sequence-regulated copolymerization based on periodic covalent positioning of monomers along one-dimensional nanochannels
Nat. Commun. 2018, 9, 329.

Transcription of Chirality from Metal-Organic Framework to Polythiophene
J. Am. Chem. Soc. 2019, 141, 19565-19569.

Scalable and Precise Synthesis of Armchair-Edge Graphene Nanoribbon in Metal–Organic Framework 
J. Am. Chem. Soc. 2020, 142, 5509-5514.

Fabrication of Double-Stranded Vinyl Polymers Mediated by Coordination Nanochannels 
J. Am. Chem. Soc. 2023, 145, 2448-2454.

Synthesis of polyacene mediated by using a metal–organic framework 
Nat. Synth. 2023, 2, 848-854.

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