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PreprintCC BYChemRxiv

Molecular Origins of Lithium-Ion Transport in the Anionic Metal–Organic Framework SU-102

  • Suman Saha1,2
  • Youhan Lu1,2
  • Zhentao Yang3
  • Julius J. Oppenheim3
  • Vibhu Vardhan Singh
  • Mircea Dincă3
  • Francesco Paesani1,2,4
4 affiliations
  1. 1Department of Chemistry
  2. 2University of California San Diego
  3. 3Department of Chemistry, Princeton University, Washington Road, Princeton, New Jersey, 08540
  4. 4Materials Science and Engineering
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Abstract

Metal–organic framework (MOF) quasi-solid electrolytes offer chemically tunable environments for ion transport, but the molecular roles of framework coordination and confined solvent remain unclear. Here, we combined solid-state nuclear magnetic resonance (ssNMR) measurements with molecular dynamics simulations to determine the Li+ transport mechanism in propylene carbonate-filled SU-102. Variable-temperature direct-and cross-polarization 7Li ssNMR reveal two distinct Li+ populations with different local tumbling dynamics. Our simulations identified Zr-associated, linkerassociated, and fully PC-solvated Li+ coordination environments. We found that Zrassociated sites provide the strongest thermodynamic stabilization, whereas the sitepersistence function decays more rapidly for linker-associated Li+ over the simulated interval. The linker-associated state exhibits the largest trial-weighted displacement, and linker-to-linker hopping is the most frequent classified event under the sampled fields, followed by Zr-to-Zr hopping. Chemical color-diffusion nonequilibrium molecular dynamics yielded an ionic conductivity of 1.34 ± 0.48 mS cm−1, the same order of magnitude as the experimental value of 0.52 mS cm−1. Together, our results support a picture in which PC-assisted hopping between linker sites contributes more strongly than vehicular diffusion of fully solvated ions under the simulated conditions. These findings identify the balance between ion–framework stabilization and facile site-to-site exchange as a key design principle for reticular quasi-solid electrolytes.

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Cite

BibTeXRIS
BibTeX
@misc{saha2026molecular,
  title = {{Molecular Origins of Lithium-Ion Transport in the Anionic Metal–Organic Framework SU-102}},
  author = {Suman Saha and Youhan Lu and Zhentao Yang and Julius J. Oppenheim and Vibhu Vardhan Singh and Mircea Dincă and Francesco Paesani},
  howpublished = {ChemRxiv},
  year = {2026},
  month = aug,
  doi = {10.26434/chemrxiv.15008063/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008063/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Molecular Origins of Lithium-Ion Transport in the Anionic Metal–Organic Framework SU-102
AU  - Suman Saha
AU  - Youhan Lu
AU  - Zhentao Yang
AU  - Julius J. Oppenheim
AU  - Vibhu Vardhan Singh
AU  - Mircea Dincă
AU  - Francesco Paesani
PY  - 2026
DA  - 2026/08/31
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008063/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008063/v1
AB  - Metal–organic framework (MOF) quasi-solid electrolytes offer chemically tunable environments for ion transport, but the molecular roles of framework coordination and confined solvent remain unclear. Here, we combined solid-state nuclear magnetic resonance (ssNMR) measurements with molecular dynamics simulations to determine the Li+ transport mechanism in propylene carbonate-filled SU-102. Variable-temperature direct-and cross-polarization 7Li ssNMR reveal two distinct Li+ populations with different local tumbling dynamics. Our simulations identified Zr-associated, linkerassociated, and fully PC-solvated Li+ coordination environments. We found that Zrassociated sites provide the strongest thermodynamic stabilization, whereas the sitepersistence function decays more rapidly for linker-associated Li+ over the simulated interval. The linker-associated state exhibits the largest trial-weighted displacement, and linker-to-linker hopping is the most frequent classified event under the sampled fields, followed by Zr-to-Zr hopping. Chemical color-diffusion nonequilibrium molecular dynamics yielded an ionic conductivity of 1.34 ± 0.48 mS cm−1, the same order of magnitude as the experimental value of 0.52 mS cm−1. Together, our results support a picture in which PC-assisted hopping between linker sites contributes more strongly than vehicular diffusion of fully solvated ions under the simulated conditions. These findings identify the balance between ion–framework stabilization and facile site-to-site exchange as a key design principle for reticular quasi-solid electrolytes.
ER  -