Characterizing the Structure of Organic Molecules of Intrinsic Microporosity by Molecular Simulations and X-ray Scattering

LJ Abbott and AG McDermott and A Del Regno and RGD Taylor and CG Bezzu and KJ Msayib and NB McKeown and FR Siperstein and J Runt and CM Colina, JOURNAL OF PHYSICAL CHEMISTRY B, 117, 355-364 (2013).

DOI: 10.1021/jp308798u

The design of a new class of materials, called organic molecules of intrinsic microporosity (OMIMs), incorporates awkward, concave shapes to prevent efficient packing of molecules, resulting in microporosity. This work presents predictive molecular simulations and experimental wide- angle X-ray scattering (WAXS) for a series of biphenyl-core OMIMs with varying end-group geometries. Development of the utilized simulation protocol was based on comparison of several simulation methods to WAXS patterns. In addition, examination of the simulated structures has facilitated the assignment of WAXS features to specific intra-and intermolecular distances, making this a useful tool for characterizing the packing behavior of this class of materials. Analysis of the simulations suggested that OMIMs had greater microporosity when the molecules were the most shape-persistent, which required rigid structures and bulky end groups. The simulation protocol presented here allows for predictive, presynthesis screening of OMIMs and similar complex molecules to enhance understanding of their structures and aid in future design efforts.

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