Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 112, Issue 36, Pages 11161-11168Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1514485112
Keywords
mechanically interlocked molecules; metal-organic framework; molecular switches; rotaxanes; radicals
Categories
Funding
- Joint Center of Excellence in Integrated Nano-Systems at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU) [34-949]
- National Science Foundation (NSF) [CHE-1308107, CHE-1266201]
- US-UK Fulbright Commission
- US-Israel Fulbright Program for a Postdoctoral Fellowship
- NSF [DGE-0824162]
- National Defense Science and Engineering Graduate Fellowship from the Department of Defense [FA9550-11-C-0028]
- Department of Energy Office of Science Graduate Fellowship Program [DE-AC05-06OR23100]
- Fulbright New Zealand for a Fulbright Graduate Award
- New Zealand Federation of Graduate Women for a Postgraduate Fellowship Award
- Army Research Office [W911NF-12-1-0130, W911NF-13-1-0229]
- US Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-FG87ER13808]
- NU
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1266201] Funding Source: National Science Foundation
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The organization of trisradical rotaxanes within the channels of a Zr-6-based metal-organic framework (NU-1000) has been achieved post-synthetically by solvent-assisted ligand incorporation. Robust Zr-IV-carboxylate bonds are forged between the Zr clusters of NU-1000 and carboxylic acid groups of rotaxane precursors (semirotaxanes) as part of this building block replacement strategy. Ultraviolet-visible-near-infrared (UV-Vis-NIR), electron paramagnetic resonance (EPR), and H-1 nuclear magnetic resonance (NMR) spectroscopies all confirm the capture of redox-active rotaxanes within the mesoscale hexagonal channels of NU-1000. Cyclic voltammetry measurements performed on electroactive thin films of the resulting material indicate that redox-active viologen subunits located on the rotaxane components can be accessed electrochemically in the solid state. In contradistinction to previous methods, this strategy for the incorporation of mechanically interlocked molecules within porous materials circumvents the need for de novo synthesis of a metal-organic framework, making it a particularly convenient approach for the design and creation of solid-state molecular switches and machines. The results presented here provide proof-of-concept for the application of postsynthetic transformations in the integration of dynamic molecular machines with robust porous frameworks.
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