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Spatially resolved analysis of short-range structure perturbations in a plastically bent molecular crystal

Nature Chemistry volume 7, pages 65–72 (2015)Cite this article

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Abstract

The exceptional mechanical flexibility observed with certain organic crystals defies the common perception of single crystals as brittle objects. Here, we describe the morphostructural consequences of plastic deformation in crystals of hexachlorobenzene that can be bent mechanically at multiple locations to 360° with retention of macroscopic integrity. This extraordinary plasticity proceeds by segregation of the bent section into flexible layers that slide on top of each other, thereby generating domains with slightly different lattice orientations. Microscopic, spectroscopic and diffraction analyses of the bent crystal showed that the preservation of crystal integrity when stress is applied on the (001) face requires sliding of layers by breaking and re-formation of halogen–halogen interactions. Application of stress on the (100) face, in the direction where π···π interactions dominate the packing, leads to immediate crystal disintegration. Within a broader perspective, this study highlights the yet unrecognized extraordinary malleability of molecular crystals with strongly anisotropic supramolecular interactions.

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Figure 1: Morphology and surface texture of an HCB crystal bent manually by the three-point method.
Figure 2: Nanoindentation at fixed load (2 mN) of two HCB crystals bent normal to the (001) face.
Figure 3: Optical micrograph and diffraction images recorded for a bent HCB crystal and the unit cell across the kink probed with a micro-X-ray beam show small changes in the unit cell upon bending.
Figure 4: Spatial vibrational spectroscopic analysis of bent crystals of HCB by micro-IR and micro-Raman spectroscopy.
Figure 5: Schematic representation of plastic bending of single crystals of HCB and the consequences at different levels of structural hierarchy.

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Acknowledgements

This work was partly carried out with financial support from New York University Abu Dhabi. The micro-X-ray diffraction and micro-IR spectroscopic measurements were performed at BL40XU (X-ray) and BL43IR (IR), SPring-8, with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposals nos. 2013A1052 (X-ray) and 2014A1826 (IR)). The authors thank J. Weston (New York University Abu Dhabi) for his help with the nanoindentation and AFM experiments, A. Basu (IISER Kolkata) for assisting with the micro-Raman spectra and J. Whelan for comments on the manuscript.

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Author notes

  1. Manas K. Panda and Soumyajit Ghosh: These authors contributed equally to this work

Authors and Affiliations

  1. New York University Abu Dhabi, Abu Dhabi, PO Box 129188, United Arab Emirates

    Manas K. Panda & Panče Naumov

  2. Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur Campus, Mohanpur, 741 246, India

    Soumyajit Ghosh & C. Malla Reddy

  3. Japan Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo, Sayo, 679-5198, Hyogo, Japan

    Nobuhiro Yasuda & Taro Moriwaki

  4. Department of Physical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur Campus, Mohanpur, 741 252, India

    Goutam Dev Mukherjee

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Contributions

M.K.P. performed the nanoindentation tests and other characterization, and analysed the data. S.G. and G.D.M. recorded and analysed the Raman spectra. N.Y. recorded and analysed the micro-X-ray diffraction data. T.M. recorded the infrared spectra. P.N. and C.M.R. conceived the study, partially analysed the data and co-wrote the paper. The manuscript was written with contributions from all authors. All authors have given approval to the final version of the manuscript.

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Correspondence to C. Malla Reddy or Panče Naumov.

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Panda, M., Ghosh, S., Yasuda, N. et al. Spatially resolved analysis of short-range structure perturbations in a plastically bent molecular crystal. Nature Chem 7, 65–72 (2015). https://doi.org/10.1038/nchem.2123

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