Understanding DABCO Nanorotor Dynamics and Water Effects in Isostructural Metal-Organic Frameworks

Flexible framework dynamics present in the subset of metal-organic frameworks known as soft porous crystals gives rise to interesting structural properties that are unique to this class of materials. In this work we use experiments and molecular simulation to provide insight into the highly dynamic nanorotor behavior of the DABCO (1,4-diazabicyclo[2.2.2]

octane) ligand in the pillared Zn-DMOF and Zn-DMOF-TM structures. While DABCO is known to be displaced in the presence of water in the parent Zn-DMOF structure, the Zn-DMOF-TM variation is highly stable even after adsorbing significant amounts of water vapor.[1] The dynamics of DABCO in the presence of water guest molecules is therefore also explored in the Zn-DMOF-TM structure via in-situ experiments along with molecular simulation.
This analysis not only provides fundamental insight into the inherent and guest-induced intraframework dynamics in these structures but also has implications in understanding the mechanism of water stability within these materials, an important criterion in the evaluation of metal-organic frameworks for real world applications.[2]

[1] H. Jasuja, N. Burtch, Y.G. Huang, Y. Cai, K. Walton, Langmuir. 29 (2013) 633-642.
[2] N. Burtch, H. Jasuja, K. Walton, Chem. Rev. DOI: 10.1021/cr5002589.

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