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Title: Ultrafast rotation in an amphidynamic crystalline metal organic framework

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
 [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)
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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.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1427926
Report Number(s):
PNNL-SA-125469; 45292; KP1704020
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Vol. 114, Issue 52; ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 70 works
Citation information provided by
Web of Science

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Cited By (18)

Precessional Motion in Crystalline Solid Solutions of Ionic Rotors journal September 2018
A de novo strategy for predictive crystal engineering to tune excitonic coupling journal May 2019
Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals journal October 2019
Libration of phenyl groups detected by VT-SSNMR: Comparison with X-ray crystallography journal June 2018
Exploiting rotational motion in molecular crystals journal January 2018
Dynamic Motion of Organic Ligands in Polar Layered Cobalt Phosphonates journal August 2018
Atomistic structures and dynamics of prenucleation clusters in MOF-2 and MOF-5 syntheses journal August 2019
Unidirectional rotary motion in a metal–organic framework journal March 2019
Ultrafast Melting of Metal–Organic Frameworks for Advanced Nanophotonics journal December 2019
Nanoscale rotational dynamics of four independent rotators confined in crowded crystalline layers journal January 2020
Fast motion of molecular rotors in metal–organic framework struts at very low temperatures journal July 2020
Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks text January 2019
Rotational Dynamics of Linkers in Metal–Organic Frameworks journal March 2019
Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks journal January 2019
Anisotropic Thermal Expansion as the Source of Macroscopic and Molecular Scale Motion in Phosphorescent Amphidynamic Crystals journal October 2019
A de novo strategy for predictive crystal engineering to tune excitonic coupling text January 2019
Atomistic structures and dynamics of prenucleation clusters in MOF-2 and MOF-5 syntheses journal August 2019
A de novo strategy for predictive crystal engineering to tune excitonic coupling text January 2019

Figures / Tables (6)

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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