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Title: Ultrafast rotation in an amphidynamic crystalline metal organic framework

Amphidynamic crystals are an emergent class of condensed phase matter designed with a combination of lattice-forming elements linked to components that display engineered dynamics in the solid state. Here, we address the design of a crystalline array of molecular rotors with inertial diffusional rotation at the nanoscale, characterized by the absence of steric or electronic barriers. We solved this challenge with 1,4-bicyclo[2.2.2]octane dicarboxylic acid (BODCA)-MOF, a metal-organic framework (MOF) built with a high-symmetry bicyclo[2.2.2]octane dicarboxylate linker in a Zn 4O cubic lattice. Using spin-lattice relaxation 1H solid-state NMR at 29.49 and 13.87 MHz in the temperature range of 2.3–80 K, we showed that internal rotation occurs in a potential with energy barriers of 0.185 kcal mol -1. These results were confirmed with 2H solid-state NMR line-shape analysis and spin-lattice relaxation at 76.78 MHz obtained between 6 and 298 K, which, combined with molecular dynamics simulations, indicate that inertial diffusional rotation is characterized by a broad range of angular displacements with no residence time at any given site. Furthermore, the ambient temperature rotation of the bicyclo[2.2.2]octane (BCO) group in BODCA-MOF constitutes an example where engineered rotational dynamics in the solid state are as fast as they would be in a high-densitymore » gas or in a low-density liquid phase.« less
Authors:
 [1] ;  [2] ; ORCiD logo [3] ;  [1] ;  [1] ;  [1] ; ORCiD logo [1]
  1. Univ. of California, Los Angeles, CA (United States)
  2. Univ. of Central Florida, Orlando, FL (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Report Number(s):
PNNL-SA-125469
Journal ID: ISSN 0027-8424; 45292; KP1704020
Grant/Contract Number:
AC05-76RL01830
Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 52; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Environmental Molecular Sciences Laboratory; metal-organic frameworks; molecular rotors; molecular machines; smart materials; amphidynamic crystals
OSTI Identifier:
1427926

Vogelsberg, Cortnie S., Uribe-Romo, Fernando J., Lipton, Andrew S., Yang, Song, Houk, K. N., Brown, Stuart, and Garcia-Garibay, Miguel A.. Ultrafast rotation in an amphidynamic crystalline metal organic framework. United States: N. p., Web. doi:10.1073/pnas.1708817115.
Vogelsberg, Cortnie S., Uribe-Romo, Fernando J., Lipton, Andrew S., Yang, Song, Houk, K. N., Brown, Stuart, & Garcia-Garibay, Miguel A.. Ultrafast rotation in an amphidynamic crystalline metal organic framework. United States. doi:10.1073/pnas.1708817115.
Vogelsberg, Cortnie S., Uribe-Romo, Fernando J., Lipton, Andrew S., Yang, Song, Houk, K. N., Brown, Stuart, and Garcia-Garibay, Miguel A.. 2017. "Ultrafast rotation in an amphidynamic crystalline metal organic framework". United States. doi:10.1073/pnas.1708817115.
@article{osti_1427926,
title = {Ultrafast rotation in an amphidynamic crystalline metal organic framework},
author = {Vogelsberg, Cortnie S. and Uribe-Romo, Fernando J. and Lipton, Andrew S. and Yang, Song and Houk, K. N. and Brown, Stuart and Garcia-Garibay, Miguel A.},
abstractNote = {Amphidynamic crystals are an emergent class of condensed phase matter designed with a combination of lattice-forming elements linked to components that display engineered dynamics in the solid state. Here, we address the design of a crystalline array of molecular rotors with inertial diffusional rotation at the nanoscale, characterized by the absence of steric or electronic barriers. We solved this challenge with 1,4-bicyclo[2.2.2]octane dicarboxylic acid (BODCA)-MOF, a metal-organic framework (MOF) built with a high-symmetry bicyclo[2.2.2]octane dicarboxylate linker in a Zn4O cubic lattice. Using spin-lattice relaxation 1H solid-state NMR at 29.49 and 13.87 MHz in the temperature range of 2.3–80 K, we showed that internal rotation occurs in a potential with energy barriers of 0.185 kcal mol-1. These results were confirmed with 2H solid-state NMR line-shape analysis and spin-lattice relaxation at 76.78 MHz obtained between 6 and 298 K, which, combined with molecular dynamics simulations, indicate that inertial diffusional rotation is characterized by a broad range of angular displacements with no residence time at any given site. Furthermore, the ambient temperature rotation of the bicyclo[2.2.2]octane (BCO) group in BODCA-MOF constitutes an example where engineered rotational dynamics in the solid state are as fast as they would be in a high-density gas or in a low-density liquid phase.},
doi = {10.1073/pnas.1708817115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 52,
volume = 114,
place = {United States},
year = {2017},
month = {12}
}

Works referenced in this record:

Modular Chemistry: Secondary Building Units as a Basis for the Design of Highly Porous and Robust Metal−Organic Carboxylate Frameworks
journal, April 2001
  • Eddaoudi, Mohamed; Moler, David B.; Li, Hailian
  • Accounts of Chemical Research, Vol. 34, Issue 4, p. 319-330
  • DOI: 10.1021/ar000034b

Amphidynamic Character of Crystalline MOF-5: Rotational Dynamics of Terephthalate Phenylenes in a Free-Volume, Sterically Unhindered Environment
journal, March 2008
  • Gould, Stephanie L.; Tranchemontagne, David; Yaghi, Omar M.
  • Journal of the American Chemical Society, Vol. 130, Issue 11, p. 3246-3247
  • DOI: 10.1021/ja077122c

Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
journal, January 2002
  • Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel
  • Science, Vol. 295, Issue 5554, p. 469-472
  • DOI: 10.1126/science.1067208

Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999
  • Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
  • Nature, Vol. 402, Issue 6759, p. 276-279
  • DOI: 10.1038/46248