Impact of Shape Persistence on the Porosity of Molecular Cages

Timothy P. Moneypenny, Nathan P. Walter, Zhikun Cai, Yu Run Miao, Danielle L. Gray, Jordan J. Hinman, Semin Lee, Yang Zhang, Jeffrey S. Moore

Research output: Contribution to journalArticlepeer-review


Porous materials provide a plethora of technologically important applications that encompass molecular separations, catalysis, and adsorption. The majority of research in this field involves network solids constructed from multitopic constituents that, when assembled either covalently or ionically, afford macromolecular arrangements with micro- or meso-porous apertures. Recently, porous solids fabricated from discrete organic cages have garnered much interest due to their ease of handling and solution processability. Although this class of materials is a promising alternative to network solids, fundamental studies are still required to elucidate critical structure-function relationships that govern microporosity. Here, we report a systematic investigation of the effects of building block shape-persistence on the porosity of molecular cages. Alkyne metathesis and edge-specific postsynthetic modifications afforded three organic cages with alkynyl, alkenyl, and alkyl edges, respectively. Nitrogen adsorption experiments conducted on rapidly crystallized and slowly crystallized solids illustrated a general trend in porosity: alkynyl > alkenyl > alkyl. To understand the molecular-scale origin of this trend, we investigated the short and long time scale molecular motions of the molecular cages using ab initio molecular dynamics (AIMD) and classical molecular dynamics (MD) simulations. Our combined experimental and computational results demonstrate that the microporosity of molecular cages directly correlates with shape persistence. These findings discern fundamental molecular requirements for rationally designing porous molecular solids.

Original languageEnglish (US)
Pages (from-to)3259-3264
Number of pages6
JournalJournal of the American Chemical Society
Issue number8
StatePublished - Mar 1 2017

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Impact of Shape Persistence on the Porosity of Molecular Cages'. Together they form a unique fingerprint.

Cite this