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

Qiang Zhu, Jay Johal, Daniel E. Widdowson, Zhongfu Pang, Boyu Li, Christopher M. Kane, Vitaliy Kurlin*, Graeme M. Day*, Marc A. Little*, Andrew I. Cooper*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

35 Citations (Scopus)
8 Downloads (Pure)

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 a priori 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–3) mesoporous hydrogen-bonded framework (HOF), 3D-CageHOF-1. This structure comprises an organic cage (Cage-3-NH2) that was predicted to form kinetically trapped, low-density polymorphs via CSP. Pointwise distance distribution structural invariants revealed five predicted forms of Cage-3-NH2 that are analogous to experimentally realized porous crystals of a chemically different but geometrically similar molecule, T2. 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.
Original languageEnglish
Pages (from-to)9893-9901
Number of pages9
JournalJournal of the American Chemical Society
Volume144
Issue number22
Early online date29 May 2022
DOIs
Publication statusPublished - 8 Jun 2022

Keywords

  • porous materials
  • crystallisation
  • X-ray diffraction
  • crystal engineering
  • structural invariants
  • crystal structure prediction
  • computational chemistry
  • organic cages

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