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Large negative thermal expansion of a polymer driven by a submolecular conformational change

Nature Chemistry volume 5, pages 1035–1041 (2013)Cite this article

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A Corrigendum to this article was published on 22 April 2014

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Abstract

Mechanoresponsive polymers hold great technological potential in drug delivery, ‘smart’ optical systems and microelectromechanical systems. However, hysteresis and fatigue (associated with large-scale polymer chain rearrangement) are often problematic. Here, we describe a polyarylamide film that contains s-dibenzocyclooctadiene (DBCOD), which can generate unconventional and completely reversible thermal contraction under low-energy stimulation. The films exhibit a giant negative thermal expansion coefficient of approximately −1,200 ppm K−1 at ambient or near-ambient temperatures, much higher than any known negative-thermal-expansion materials under similar operating conditions. Mechanical characterization, calorimetry, spectroscopic analysis and density-functional theory calculations all point to the conformational change of the DBCOD moiety, from the thermodynamic global energy minimum (twist-boat) to a local minimum (chair), as the origin of this abnormal thermal shrinkage. This newly identified, low-energy-driven, thermally agile molecular subunit opens a new pathway to creating near-infrared-based macromolecular switches and motors, and for ambient thermal energy storage and conversion.

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Figure 1: Chemical structure and mechanical response behaviour under pulsed laser stimulation.
Figure 2: Tensile measurement set-up and mechanical response characterization using NIR or thermal heating as stimuli.
Figure 3: Negative thermal expansion.
Figure 4: DFT calculations and FTIR analysis of the –NH– stretching region.

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Change history

  • 22 April 2014

    In the version of this Article previously published, some incorrect data were included in Fig. 1e. The initial data were inadvertently repeated as the data for 20,000 cycles, and the total number of cycles was stated as 50,000 when it should have been 43,000. An error corresponding to the latter was also made in the first full sentence on page 1037. Figure 1e should have appeared as shown above. These errors have been corrected in the online versions of the Article.

  • 22 April 2014

    Nature Chemistry 5, 1035–1041 (2013); Published online 20 October 2013; corrected after print 22 April 2014. In the version of this Article previously published, some incorrect data were included in Fig. 1e. The initial data were inadvertently repeated as the data for 20,000 cycles, and the total number of cycles was stated as 50,000 when it should have been 43,000.

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Acknowledgements

The authors thank D.C. Martin for providing XTA (prepared by K. Walker, L. Markoski and G. Spilman in the laboratory of J. Moore), and C.Y.C. Lee for technical discussions. The authors acknowledge financial support from DARPA (grant no. N66001-09-1-2088), CITRIS (grant no. 73-2010), UC Merced start-up and the National Science and Technology Key Project of China (2012AA020204).

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Authors and Affiliations

  1. Materials Science and Engineering, School of Engineering, University of California at Merced, 5200 North Lake Road, Merced, 95343, California, USA

    Xingyuan Shen, Christopher Viney & Jennifer Q. Lu

  2. Department of Chemistry and Chemical Biology, School of Natural Sciences, University of California at Merced, 5200 North Lake Road, Merced, 95343, California, USA

    Erin R. Johnson

  3. State Key Laboratory of Molecular Engineering of Polymers and Department of Macromolecular Science, Laboratory of Advanced Materials, Fudan University, 220 Han Dan Road, Shanghai, 200433, China

    Xingyuan Shen & Changchun Wang

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  1. Xingyuan Shen
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  5. Jennifer Q. Lu
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Contributions

J.Q.L. designed the polymer system, developed the NTE concept, designed the experiments and oversaw the project. C.V. conceived that cyclooctane is an unconstrained unit and designed the mechanical tests. The synthesis strategy was developed by C.C.W., X.S. and J.Q.L. and was performed and refined by X.S. Films were prepared by X.S. Mechanical characterization apparatus was designed by C.V. and performed by X.S., mainly with help from C.V. Data were analysed by J.Q.L. with help from E.R.J. and X.S. Quantum chemical calculations were carried out by E.R.J. The manuscript was prepared by J.Q.L. with help from E.R.J., C.V., C.C.W. and X.S.

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Correspondence to Jennifer Q. Lu.

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The authors declare no competing financial interests.

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Shen, X., Viney, C., Johnson, E. et al. Large negative thermal expansion of a polymer driven by a submolecular conformational change. Nature Chem 5, 1035–1041 (2013). https://doi.org/10.1038/nchem.1780

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