Analogy Powered by Prediction and Structural Invariants: Computationally Led Discovery of a Mesoporous Hydrogen-Bonded Organic Cage Crystal



Zhu, Qiang, Johal, Jay, Widdowson, Daniel E, Pang, Zhongfu, Li, Boyu, Kane, Christopher M, Kurlin, Vitaliy, Day, Graeme M, Little, Marc A and Cooper, Andrew I
(2022) Analogy Powered by Prediction and Structural Invariants: Computationally Led Discovery of a Mesoporous Hydrogen-Bonded Organic Cage Crystal. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 144 (22). pp. 9893-9901.

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Abstract

Mesoporous molecular crystals have potential applications in separation and catalysis, but they are rare and hard to design because many weak interactions compete during crystallization, and most molecules have an energetic preference for close packing. Here, we combine crystal structure prediction (CSP) with structural invariants to continuously qualify the similarity between predicted crystal structures for related molecules. This allows isomorphous substitution strategies, which can be unreliable for molecular crystals, to be augmented by <i>a priori</i> prediction, thus leveraging the power of both approaches. We used this combined approach to discover a rare example of a low-density (0.54 g cm<sup>-3</sup>) mesoporous hydrogen-bonded framework (HOF), <b>3D-CageHOF-1</b>. This structure comprises an organic cage (<b>Cage-3-NH</b><sub><b>2</b></sub>) that was predicted to form kinetically trapped, low-density polymorphs <i>via</i> CSP. Pointwise distance distribution structural invariants revealed five predicted forms of <b>Cage-3-NH</b><sub><b>2</b></sub> that are analogous to experimentally realized porous crystals of a chemically different but geometrically similar molecule, <b>T2</b>. More broadly, this approach overcomes the difficulties in comparing predicted molecular crystals with varying lattice parameters, thus allowing for the systematic comparison of energy-structure landscapes for chemically dissimilar molecules.

Item Type: Article
Uncontrolled Keywords: 3402 Inorganic Chemistry, 3403 Macromolecular and Materials Chemistry, 34 Chemical Sciences, 7 Affordable and Clean Energy
Divisions: Faculty of Science and Engineering > School of Electrical Engineering, Electronics and Computer Science
Faculty of Science and Engineering > School of Physical Sciences
Depositing User: Symplectic Admin
Date Deposited: 07 Jul 2022 11:49
Last Modified: 20 Jun 2024 16:31
DOI: 10.1021/jacs.2c02653
Open Access URL: https://doi.org/10.1021/jacs.2c02653
Related URLs:
URI: https://livrepository.liverpool.ac.uk/id/eprint/3157942