Unidirectional compression and expansion of a crosslinked MOF crystal prepared via axis-dependent crosslinking and ligand exchange

• Published in: Polymer journal Vol. 49; no. 9; pp. 685 - 689
• Main Authors: Kokado, Kenta, Ishiwata, Takumi, Anan, Shizuka, Sada, Kazuki
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.09.2017; Nature Publishing Group
• Subjects: 639/638/298/921; 639/638/455/941; 639/638/455/955; 639/638/455/960; Biomaterials; Bioorganic Chemistry; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Construction methods; Crosslinking; Crystals; Deformation; Drying; Exchanging; Formability; Ligands; Mechanical devices; Metal-organic frameworks; original-article; Polymer chemistry; Polymer Sciences; Polymerization; Solvents; Submerging; Surfaces and Interfaces; Thin Films
• DOI: 10.1038/pj.2017.32
• ISSN: 0032-3896

The artificial construction of anisotropic deforming materials is one of the great challenges in materials and polymer chemistry. In this paper, we demonstrate a unidirectionally deformable material with reversibility. First, crystal crosslinking of a pillared-layer metal–organic framework (PLMOF) was accomplished, followed by the exchange of the pillar ligand with the monotopic ligand. The obtained crosslinked MOF crystal showed reversible unidirectional compression and expansion during cycles of drying and immersion in good solvents. The macroscopic unidirectional deformation was derived from microscopic variations in the layer distance in the MOF crystal. The polymerization between the organic ligand and the crosslinker effectively reinforced the MOF crystal, which had enough durability for reversible unidirectional deformation. Our strategy is a promising general method for the construction of anisotropic deforming materials, which are often seen in biological systems and mechanical devices. An unidirectionally deformable material with reversibility was achieved. The method relies on crystal crosslinking of pillared-layer metal–organic framework (PLMOF), followed by exchange of the pillar ligand to monotopic ligand. The obtained crosslinked MOF crystal exhibited reversibly unidirectional compression and expansion upon cycles of drying and immersion in good solvents. The preservation of layer structure enabled to confirm the unidirectional deformation not only macroscopically but also microscopically. Our strategy will be a promising general method for construction of anisotropic deforming materials, which can be often seen in biological systems or mechanical devices.