Lattice Expansion and Contraction in Metal-Organic Frameworks by Sequential Linker Reinstallation

Isoreticular expansion of metal-organic frameworks (MOFs) by linker elongation often leads to interpenetration or other undesired structures. Here we report a sequential linker labilization and reinstallation method to expand the unit cell dimensions of MOFs while manipulating the framework structure and interpenetration. A stable Zr-based MOF was initially synthesized as a template. Subsequently, labile linkers with imine bonds were post-synthetically introduced into the structure to destabilize the Zr-MOF. Eventually, gradual dissociation of the imine-based linkers and reinstallation of longer linkers into the defective spaces lead to the formation of non-interpenetrated isoreticular Zr-MOFs with progressively increased pore sizes. Similarly, lattice contraction can also be realized by incorporating shorter linkers. In addition to providing a powerful tool that yields control over the structures and functions of MOFs, this work also highlights new opportunities by combining the dynamic covalent chemistry with coordination chemistry in MOFs.

Duke Scholars

Author Liang Feng Thomas Lord Department of Mechanical Engineering and Materia ...