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ChemComm
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DOI: 10.1039/C8CC04292F
COMMUNICATION
Journal Name
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4a). This is a similar finding to the NMR results. The MD results
further show that the side-chains have apparent larger mean
squared deviation (MSD) because the side chains can move
back and forth and up and down inside the pore, which turns
into a larger apparent diffusion coefficient (see the videos in
the SI). The trajectories also show that this is not a pure
classical Brownian motion. The ideal Brownian motion is
expected as:
a) Z. Dominguez, H. Dang, M. J. Strouse and M. A. Garcia-
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ꢀꢁꢂ ∝ ꢂ ⋅ ꢃ
(2)
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where D is the diffusion coefficient and t is time; however,
there are regions in the trajectory of the side chains and the
even the backbone atom that suggest anomalous diffusion.
The details of this behaviour are beyond the scope of this
work; nonetheless, we were able to obtain the diffusion
coefficient of the ideal region (Figure 4b). Notice the order of
order of magnitude difference between the side chains (10-7
cm2 s-1) versus the backbone carbons (10-8 cm2 s-1). This is to
best of our knowledge the first time this behaviour is observed
and characterized in a COF.
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In summary, we prepared a family of covalent organic
frameworks that have been functionalized with oligo-ethylene
oxide side-chains to probe the differences in amphidynamic
behaviour between the organic framework and the side-chain.
We observed through solid-state NMR measurements that the
crystalline COFs exhibit the expected amphidynamic behaviour
allowing to probe the effects of the various functional groups
systematically with easy synthesis methods. The MD
simulations further show that the atomistic behaviour of the
side chain is different than the backbone atoms, thus
predicting different apparent diffusion coefficients. The values
for the diffusion coefficient are in the range of Li diffusion in
some graphite systems which makes them promising
candidates for transport applications, especially as solid-state
electrolytes for all-solid-state Li-ion batteries. Taking
advantage of unique features in COFs—tuneable porosity,
modularity, and predictability of crystal packing—can provide
an insight to understanding how dynamic processes in organic
solids can be controlled and designed.
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FJU-R would like to acknowledge the UCF College of
Sciences and Office of Research and Commercialization for
funds, JKH would like to thank the National Science Foundation
(grant no. CHE-14551592) for funds. JLM-C gratefully
acknowledges support from the Energy and Materials Initiative
at FSU for funds and its High-Performance Computer (HPC) for
computational resources and support.
Conflicts of interest
There are no conflicts to declare.
Notes and references
‡ See Supplementary Information.
§ Although, polymorphism cannot be ruled out.
1
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4 | J. Name., 2012, 00, 1-3
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