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Title: Ultrafast rotation in an amphidynamic crystalline metal organic framework

Abstract

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 ormore » in a low-density liquid phase.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [1];  [1];  [1]; ORCiD logo [1]
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  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:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1427926
Report Number(s):
PNNL-SA-125469
Journal ID: ISSN 0027-8424; 45292; KP1704020
Grant/Contract Number:  
AC05-76RL01830
Resource 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)
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

Citation Formats

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., 2017. Web. doi:10.1073/pnas.1708817115.
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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. https://doi.org/10.1073/pnas.1708817115
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Vogelsberg, Cortnie S., Uribe-Romo, Fernando J., Lipton, Andrew S., Yang, Song, Houk, K. N., Brown, Stuart, and Garcia-Garibay, Miguel A. Tue . "Ultrafast rotation in an amphidynamic crystalline metal organic framework". United States. https://doi.org/10.1073/pnas.1708817115. https://www.osti.gov/servlets/purl/1427926.
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@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 = {Tue Dec 26 00:00:00 EST 2017},
month = {Tue Dec 26 00:00:00 EST 2017}
}
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Journal Article:
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https://doi.org/10.1073/pnas.1708817115
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Figures / Tables:

Figure 1 Figure 1: Isostructural networks of MOF-5 and BODCA-MOF with the corresponding BDC and BODCA rotators shown in red and the static carboxylate and Zn4O clusters shown in blue (hydrogen atoms omitted for clarity).
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    Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks
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    Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals
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    text, January 2019

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