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Dipolar order in an amphidynamic crystalline metal–organic framework through reorienting linkers

Nature Chemistry volume 13, pages 278–283 (2021)Cite this article

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Abstract

Amphidynamic crystals, which possess crystallinity and support dynamic behaviours, are very well suited to the exploration of emergent phenomena that result from the coupling on the dynamic moieties. Here, dipolar rotors have been embedded in a crystalline metal–organic framework. The material consists of Zn(ii) nodes and two types of ditopic bicyclo[2.2.2]octane-based linkers—one that coordinates to the Zn clusters through two 1,4-aza moieties, and a difluoro-functionalized derivative (the dipolar rotor) that coordinates through linked 1,4-dicarboxylate groups instead. Upon cooling, these linkers collectively order as a result of correlated dipole–dipole interactions. Variable-temperature, frequency-dependent dielectric measurements revealed a transition temperature Tc = 100 K, when a rapidly rotating, dipole-disordered, paraelectric phase transformed into an ordered, antiferroelectric one in which the dipole moments of the rotating linkers largely cancelled each other. Monte Carlo simulations on a two-dimensional rotary lattice showed a ground state with an Ising symmetry and the effects of dipole–lattice and dipole–dipole interactions.

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Fig. 1: Spontaneous broken symmetry on dipolar lattices, and the proposed manifestation in (F2-BODCA)-MOF.
Fig. 2: Structural elements of the crystal and rotator.
Fig. 3: Complex dielectric response of (F2-BODCA)-MOF.
Fig. 4: Temperature dependence of dynamical time scale of (F2-BODCA)-MOF, extracted from dielectric and NMR measurements.
Fig. 5: Results of DFT calculations.
Fig. 6: Results of Monte Carlo simulation.

Data availability

The data that support the findings of this study can be accessed at https://www.pa.ucla.edu/content/crystalline-dipolar-rotors.html. Additional information is available from the corresponding authors upon reasonable request. Crystallographic data for the structure of (F2-BODCA)-MOF reported in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition number CCDC 2034730. Source data are provided with this paper.

Code availability

The code that supports the findings of this study can be accessed at https://github.com/andrewstanton1/Metropolis-Algorithm-for-rotor-lattice.

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Acknowledgements

This material is based on work supported by the National Science Foundation under grant numbers DMR-2004553, DMR-1709304, DMR-1700471 and MRI-1532232 (solid-state NMR).

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Author notes

  1. These authors contributed equally: Y.-S. Su, E. S. Lamb, I. Liepuoniute.

Authors and Affiliations

  1. Department of Physics and Astronomy, University of California, Los Angeles, Los Angeles, CA, USA

    Y.-S. Su, E. S. Lamb, A. Chronister, A. L. Stanton, P. Guzman & S. E. Brown

  2. Department of Materials Science and Engineering, University of California, Los Angeles, Los Angeles, CA, USA

    Y.-S. Su

  3. Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, USA

    I. Liepuoniute, S. Pérez-Estrada, T. Y. Chang, K. N. Houk & M. A. Garcia-Garibay

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Contributions

S.P.-E. and M.A.G.-G. conceived of the material synthesis, and S.P.-E. and T.Y.C. synthesized the samples. M.A.G.-G., S.P.-E. and S.E.B. conceived of the dielectric measurement, E.S.L. and P.G. built the capacitance measurement probe, E.S.L. carried out the measurement, and Y.-S.S. and S.E.B. analysed the results. Y.-S.S. implemented the cryogenic NMR measurements. A.L.S. constructed the Monte Carlo code from scratch and executed the simulation with the guidance of Y.-S.S., A.C. and S.E.B. I.L. and K.N.H. performed the DFT calculations. I.L. wrote about DFT and materials synthesis. Y.-S.S. and S.E.B. coordinated the concerted efforts. Y.-S.S., S.E.B. and M.A.G.-G. wrote the manuscript with contributions from all the other authors.

Corresponding authors

Correspondence to Y.-S. Su, I. Liepuoniute, M. A. Garcia-Garibay or S. E. Brown.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–34 and Discussion.

Supplementary Data 1

Crystallographic data for (F2-BODCA)-MOF.

Source data

Source Data Fig. 3

Statistical Source Data.

Source Data Fig. 4

Statistical Source Data.

Source Data Fig. 5

Statistical Source Data.

Source Data Fig. 6

Statistical Source Data.

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Su, YS., Lamb, E.S., Liepuoniute, I. et al. Dipolar order in an amphidynamic crystalline metal–organic framework through reorienting linkers. Nat. Chem. 13, 278–283 (2021). https://doi.org/10.1038/s41557-020-00618-6

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