Does Thermosalient Effect Have to Concur with a Polymorphic Phase Transition? The Case of Methscopolamine Bromide

Klaser, Teodoro; Popović, Jasminka; Fernandes, José A.; Tarantino, Serena C.; Zema, Michele; Skoko, Željko

doi:10.3390/cryst8070301

Cited by 16 publications

(10 citation statements)

References 19 publications

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“…Instead, it could be due to non-uniform or sudden heating. A recent report of a TS behavior of the organic compound methscopolamine bromide observed motion that was not accompanied by a detectable phase transition, and this effect was attributed to unusually large anisotropic thermal expansion with coefficients of 135 (1) Â 10 À6 K À1 and 114 (1) Â 10 À6 K À1 along the a and c axes, respectively (Klaser et al, 2018). Although such behavior cannot be attributed to a TS effect (which is strictly related to a phase transition), it could nevertheless account for the observed motion of the crystals.…”

Section: Resultsmentioning

confidence: 98%

Extraordinary anisotropic thermal expansion in photosalient crystals

Yadava

Gallo

Bette

et al. 2020

IUCrJ

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Although a plethora of metal complexes have been characterized, those having multifunctional properties are very rare. This article reports three isotypical complexes, namely [Cu(benzoate)L 2], where L = 4-styrylpyridine (4spy) (1), 2′-fluoro-4-styrylpyridine (2F-4spy) (2) and 3′-fluoro-4-styrylpyridine (3F-4spy) (3), which show photosalient behavior (photoinduced crystal mobility) while they undergo [2+2] cycloaddition. These crystals also exhibit anisotropic thermal expansion when heated from room temperature to 200°C. The overall thermal expansion of the crystals is impressive, with the largest volumetric thermal expansion coefficients for 1, 2 and 3 of 241.8, 233.1 and 285.7 × 10−6 K−1, respectively, values that are comparable to only a handful of other reported materials known to undergo colossal thermal expansion. As a result of the expansion, their single crystals occasionally move by rolling. Altogether, these materials exhibit unusual and hitherto untapped solid-state properties.

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Section: Resultsmentioning

confidence: 98%

Extraordinary anisotropic thermal expansion in photosalient crystals

Yadava

Gallo

Bette

et al. 2020

IUCrJ

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“…The phenomenon is more common than it was originally thought, and there are now more than 30 documented compounds. (Examples are given in refs − .) The mechanism is not completely understood; however, it is known that it is consistently due to a very rapid, martensitic phase transition.…”

Section: Unconventional Properties Of Dynamic Crystalsmentioning

confidence: 99%

The Rise of the Dynamic Crystals

et al. 2020

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The anticipated shift in the focal point of interest of solid-state chemists, crystal engineers, and crystallographers from structure to properties to function parallels the need to apply our accumulated understanding of the intricacies of crystal structure to explaining the related properties, with the ultimate goal of harnessing that knowledge in applications that require soft, lightweight, or biocompatible organic solids. In these developments, the adaptive molecular crystals warrant particular attention as an alternative choice of materials for light, flexible, and environmentally benign devices, primarily memories, capacitors, sensors, and actuators. Some of the outstanding requirements for the application of these dynamic materials as high-efficiency energy-storage devices are strongly induced polarization, a high switching field, and narrow hysteresis in the case of reversible dynamic processes. However, having been studied almost exclusively by chemists, molecular crystals still lack the appropriate investigations that reliably evaluate their reproducibility, scalability, and actuating performance, and some important drawbacks have diverted the interest of engineers from these materials in applications. United under the umbrella term crystal adaptronics, the recent research efforts aim to realistically assess the appositeness of dynamic crystals for applications that require fast, reversible, and continuous operation over prolonged periods of time. With the aim of highlighting the most recent developments, this Perspective discusses their assets and pitfalls. It also provides some hints on the likely future developments that capitalize on the untapped, sequestered potential of this distinct materials class for applications.

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“…Typical values for molecular crystals are in the range 0-20 Â 10 À6 K À1 (Krishnan et al, 1979). Form (I) of tapentadol hydrochloride shows a negative thermal expansion and two unusually high-strain axes, properties shared by all known TM materials (Klaser et al, 2018). Thermosalient behaviour was also observed upon cooling form (II) and going through the transformation into form (I).…”

Section: Figurementioning

confidence: 93%

“…TMs include a large variety of compound types, such as organic molecules, organometallic compounds, metal complexes etc. All of them share the inescapable property of converting thermal energy into mechanical energy in the crystalline state, but, in addition, most are also characterized by some further concomitant features, sometimes believed to be part of their very essence (Klaser et al, 2018), for example: (i) they present a first-order phase transition associated with a sudden change of cell parameters and (ii) they show a negative thermal expansion in at least one direction.…”

Section: Figurementioning

confidence: 99%

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Thermal, spectroscopic and structural analysis of a thermosalient phase transformation in tapentadol hydrochloride

Gaztañaga

Baggio

Halac

et al. 2019

Acta Crystallogr Sect B

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Presented herein are detailed optical, thermal, spectroscopic and structural analyses of the phase transformation occurring in tapentadol hydrochloride (C 14 H 24 NO + ÁCl À ), a phenomenon already reported [Fischer et al. (2006); Patent: WO 2006000441 A2]. The thermal behaviour of the compound was studied using single-crystal X-ray diffraction, differential scanning calorimetry and Raman scattering measurements. The compound undergoes a first-order reversible phase transition at T heat = 318.0 (1) K, T cool = 300.0 (1) K, as assessed by the coexistence of both phases in the vicinity of the transition and the abrupt changes observed in the unit-cell parameters with temperature. The process is accompanied by clear thermosalient behaviour, with a conspicuous movement of the samples. On cooling, the transformation leads from a P2 1 2 1 2 1 symmetry (Z 0 = 1) to P2 1 , with an abrupt change in [90 $ 94.78 (1) ] and duplication of the asymmetric unit contents (Z 0 = 2). The main structural differences observed across the transition are extremely small, with almost no changes in the stronger, non-covalent interaction scheme involving the 'conventional' (N-HÁ Á ÁCl, O-HÁ Á ÁCl) hydrogen bonds.

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Does Thermosalient Effect Have to Concur with a Polymorphic Phase Transition? The Case of Methscopolamine Bromide

Cited by 16 publications

References 19 publications

Extraordinary anisotropic thermal expansion in photosalient crystals

Extraordinary anisotropic thermal expansion in photosalient crystals

The Rise of the Dynamic Crystals

Thermal, spectroscopic and structural analysis of a thermosalient phase transformation in tapentadol hydrochloride

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