4.6 Article

Ultra-Fast Molecular Rotors within Porous Organic Cages

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 23, Issue 68, Pages 17217-17221

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201704964

Keywords

molecular rotors; NMR spectroscopy; porous organic cages; responsive materials; supramolecular chemistry

Funding

  1. EPSRC [EP/N004884/1, EP/M00869X/1]
  2. Royal Society
  3. EPSRC
  4. European Research Council under the European Union's Seventh Framework Programme (FP)/ERC [321156]
  5. EPSRC [EP/N004884/1, EP/M00869X/1] Funding Source: UKRI
  6. Engineering and Physical Sciences Research Council [1510930, EP/N004884/1, EP/K039687/1, EP/M00869X/1] Funding Source: researchfish

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Using variable temperature H-2 static NMR spectra and C-13 spin-lattice relaxation times (T-1), we show that two different porous organic cages with tubular architectures are ultra-fast molecular rotors. The central para-phenylene rings that frame the windows to the cage voids display very rapid rotational rates of the order of 1.2-8x10(6)Hz at 230K with low activation energy barriers in the 12-18kJmol(-1) range. These cages act as hosts to iodine guest molecules, which dramatically slows down the rotational rates of the phenylene groups (5-10x10(4)Hz at 230K), demonstrating potential use in applications that require molecular capture and release.

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