Colossal positive and negative thermal expansion and thermosalient effect in a pentamorphic organometallic martensite

Manas K. Panda; Tomče Runčevski; Subash Chandra Sahoo; Alexei A. Belik; Naba K. Nath; Robert E. Dinnebier; Panče Naumov

doi:10.1038/ncomms5811

Colossal positive and negative thermal expansion and thermosalient effect in a pentamorphic organometallic martensite

Manas K. Panda, Tomče Runčevski, Subash Chandra Sahoo, Alexei A. Belik, Naba K. Nath, Robert E. Dinnebier, Panče Naumov

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The thermosalient effect is an extremely rare propensity of certain crystalline solids for self-actuation by elastic deformation or by a ballistic event. Here we present direct evidence for the driving force behind this impressive crystal motility. Crystals of a prototypical thermosalient material, (phenylazophenyl)palladium hexafluoroacetylacetonate, can switch between five crystal structures (α - ε) that are related by four phase transitions including one thermosalient transition (α虠γ). The mechanical effect is driven by a uniaxial negative expansion that is compensated by unusually large positive axial expansion (260 × 10^-6 K^-1) with volumetric expansion coefficients (≈250 × 10^-6 K^-1) that are among the highest values reported in molecular solids thus far. The habit plane advances at ∼10⁴ times the rate observed with non-thermosalient transitions. This rapid expansion of the crystal following the phase switching is the driving force for occurrence of the thermosalient effect.

Original language	English (US)
Article number	4811
Journal	Nature communications
Volume	5
DOIs	https://doi.org/10.1038/ncomms5811
State	Published - Sep 4 2014

ASJC Scopus subject areas

General Chemistry
General Biochemistry, Genetics and Molecular Biology
General Physics and Astronomy

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title = "Colossal positive and negative thermal expansion and thermosalient effect in a pentamorphic organometallic martensite",

abstract = "The thermosalient effect is an extremely rare propensity of certain crystalline solids for self-actuation by elastic deformation or by a ballistic event. Here we present direct evidence for the driving force behind this impressive crystal motility. Crystals of a prototypical thermosalient material, (phenylazophenyl)palladium hexafluoroacetylacetonate, can switch between five crystal structures (α - ε) that are related by four phase transitions including one thermosalient transition (α虠γ). The mechanical effect is driven by a uniaxial negative expansion that is compensated by unusually large positive axial expansion (260 × 10-6 K-1) with volumetric expansion coefficients (≈250 × 10-6 K-1) that are among the highest values reported in molecular solids thus far. The habit plane advances at ∼104 times the rate observed with non-thermosalient transitions. This rapid expansion of the crystal following the phase switching is the driving force for occurrence of the thermosalient effect.",

author = "Panda, {Manas K.} and Tom{\v c}e Run{\v c}evski and {Chandra Sahoo}, Subash and Belik, {Alexei A.} and Nath, {Naba K.} and Dinnebier, {Robert E.} and Pan{\v c}e Naumov",

note = "Funding Information: This work is financially supported by funding from New York University Abu Dhabi. The computational part of this research was carried out on the High Performance Computing resources at New York University Abu Dhabi. We thank Mr Armin Schulz for collecting the µ-Raman spectra, and Dr Holger Ott and Milan Gembicky (Bruker AXS GmbH), as well as Dr Elisa Nauha for their advice on the refinement of the crystal structure of form b. We thank European Synchrotron Radiation Facility for the beamtime (proposal number CH-3887), Dr I. Watier and Mrs O.V. Magdysyuk for their assistance during the data collection, and Mrs Jane Toye for editing this manuscript. Publisher Copyright: {\textcopyright} 2014 Macmillan Publishers Limited. All rights reserved.",

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AU - Panda, Manas K.

AU - Runčevski, Tomče

AU - Chandra Sahoo, Subash

AU - Belik, Alexei A.

AU - Nath, Naba K.

AU - Dinnebier, Robert E.

AU - Naumov, Panče

N1 - Funding Information: This work is financially supported by funding from New York University Abu Dhabi. The computational part of this research was carried out on the High Performance Computing resources at New York University Abu Dhabi. We thank Mr Armin Schulz for collecting the µ-Raman spectra, and Dr Holger Ott and Milan Gembicky (Bruker AXS GmbH), as well as Dr Elisa Nauha for their advice on the refinement of the crystal structure of form b. We thank European Synchrotron Radiation Facility for the beamtime (proposal number CH-3887), Dr I. Watier and Mrs O.V. Magdysyuk for their assistance during the data collection, and Mrs Jane Toye for editing this manuscript. Publisher Copyright: © 2014 Macmillan Publishers Limited. All rights reserved.

PY - 2014/9/4

Y1 - 2014/9/4

N2 - The thermosalient effect is an extremely rare propensity of certain crystalline solids for self-actuation by elastic deformation or by a ballistic event. Here we present direct evidence for the driving force behind this impressive crystal motility. Crystals of a prototypical thermosalient material, (phenylazophenyl)palladium hexafluoroacetylacetonate, can switch between five crystal structures (α - ε) that are related by four phase transitions including one thermosalient transition (α虠γ). The mechanical effect is driven by a uniaxial negative expansion that is compensated by unusually large positive axial expansion (260 × 10-6 K-1) with volumetric expansion coefficients (≈250 × 10-6 K-1) that are among the highest values reported in molecular solids thus far. The habit plane advances at ∼104 times the rate observed with non-thermosalient transitions. This rapid expansion of the crystal following the phase switching is the driving force for occurrence of the thermosalient effect.

AB - The thermosalient effect is an extremely rare propensity of certain crystalline solids for self-actuation by elastic deformation or by a ballistic event. Here we present direct evidence for the driving force behind this impressive crystal motility. Crystals of a prototypical thermosalient material, (phenylazophenyl)palladium hexafluoroacetylacetonate, can switch between five crystal structures (α - ε) that are related by four phase transitions including one thermosalient transition (α虠γ). The mechanical effect is driven by a uniaxial negative expansion that is compensated by unusually large positive axial expansion (260 × 10-6 K-1) with volumetric expansion coefficients (≈250 × 10-6 K-1) that are among the highest values reported in molecular solids thus far. The habit plane advances at ∼104 times the rate observed with non-thermosalient transitions. This rapid expansion of the crystal following the phase switching is the driving force for occurrence of the thermosalient effect.

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Colossal positive and negative thermal expansion and thermosalient effect in a pentamorphic organometallic martensite

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