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Alignment in Nanospaces

In general, polymer chains are randomly entangled with each other in the bulk state – properties we consider typical of them thus result from the averaged behaviors of multiple disordered chains. Arrangement of the individual polymer chains into specific conformations or assemblies should then endow them with certain enhanced mechanical, optical, electronic, and magnetic properties. Our group developed a facile methodology for controlling polymer assemblies at the molecular level by the introduction of polymers into the pores of MOFs. These encapsulated polymers can be easily isolated by the dissolution of host frameworks while maintaining the assembly structures, thereby producing unique polymeric nanomaterials, such as long-range ordered crystalline polymers, unimolecularly thick polymer monosheets, and blends of typically immiscible polymers mixed on the single nanometer scale.

Synthesis of polymer monosheets using a pillared-layer MOF



Fabrication of Two-Dimensional Polymer Arrays: Template Synthesis of Polypyrrole between Redox-Active Coordination Nanoslits
Angew. Chem. Int. Ed. 2008, 47, 9883-9886.

Highly ordered alignment of a vinyl polymer by host–guest cross-polymerization
Nat. Chem. 2013, 5, 335–341.

Mixing of immiscible polymers using nanoporous coordination templates
Nat. Commun. 2015, 6, 7473.

Unimolecularly Thick Monosheets of Vinyl Polymers Fabricated in Metal–Organic Frameworks
Nat. Commun. 2020, 11, 3573.

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