A crystal that hops in phase transition, the structure of trans,trans,anti,trans,trans-perhydropyrene

Ding, Jiahan; Herbst, R; Praefcke, Klaüs; Kohne, B.

doi:10.1107/s0108768191004500

Cited by 39 publications

(33 citation statements)

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“…29 This has been attributed to first order displacive solid-solid transition that occurs with Bain distortion. [38][39][40][41] Elastic properties in molecular solids are largely determined by the isotropy of crystal packing. 8,18 Recent studies by Ghosh and Reddy on caffeine co-crystals have established that bending of elastic organic crystals is related to isotropic packing with the presence of relatively weak and dispersive interactions in all directions.…”

Section: Introductionmentioning

confidence: 99%

Dual Stress and Thermally Driven Mechanical Properties of the Same Organic Crystal: 2,6-Dichlorobenzylidene-4-fluoro-3-nitroaniline

et al. 2015

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An elastic organic crystal, 2,6-dichlorobenzylidine-4-fluoro-3-nitroaniline (DFNA), which also shows thermosalient behavior, is studied. The presence of these two distinct properties in the same crystal is unusual and unprecedented because they follow respectively from isotropy and anisotropy in the crystal packing. Therefore, while both properties lead from the crystal structure, the mechanisms for bending and thermosalience are quite independent of one another. Crystals of the low-temperature (α) form of the title compound are bent easily without any signs of fracture with the application of deforming stress, and this bending is within the elastic limit. The crystal structure of the α-form was determined (P21/c, Z = 4, a = 3.927(7) Å, b = 21.98(4) Å, c = 15.32(3) Å). There is an irreversible phase transition at 138 °C of this form to the high-temperature β-form followed by melting at 140 °C. Variable-temperature X-ray powder diffraction was used to investigate the structural changes across the phase transition and, along with an FTIR study, establishes the structure of the β-form. A possible rationale for strain build-up is given. Thermosalient behavior arises from anisotropic changes in the three unit cell parameters across the phase transition, notably an increase in the b axis parameter from 21.98 to 22.30 Å. A rationale is provided for the existence of both elasticity and thermosalience in the same crystal. FTIR studies across the phase transition reveal important mechanistic insights: (i) increased π···π repulsions along [100] lead to expansion along the a axis; (ii) change in alignment of C-Cl and NO2 groups result from density changes; and (iii) competition between short-range repulsive (π···π) interactions and long-range attractive dipolar interactions (C-Cl and NO2) could lie at the origin of the existence of two distinctive properties.

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Section: Introductionmentioning

confidence: 99%

Dual Stress and Thermally Driven Mechanical Properties of the Same Organic Crystal: 2,6-Dichlorobenzylidene-4-fluoro-3-nitroaniline

et al. 2015

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“…Among reported organic compounds,less than two dozen of molecules have been reported to be thermosalient-active crystalline materials. [5] Figure S1 (Supporting Information) summarizes the molecular structures of reported thermosalient crystals.Ascan be seen, there does not appear to be any shared pattern among the chemical structures of thermosalient molecular crystals.W hile the detailed mechanisms of thermosalient behavior have been revealed experimentally for some crystals, [5b,d,g-l, 6] the design of such molecules as well as how they assemble to express at hermosalient effect need to be established.…”

Section: Introductionmentioning

confidence: 99%

Jumping Crystal of a Hydrogen‐Bonded Organic Framework Induced by the Collective Molecular Motion of a Twisted π System

2019

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There is alimited number of reports on mechanically responsive molecular crystals,i ncluding thermo-responsive and light-responsive crystals.Rigid ordered molecular crystals with aclose-packing structure are less able to accept distortion, which hampers the development of such molecular crystals. The thermosalient effect, or "crystal jumping", refers to athermo-responsive system that converts heat into mechanical force by thermally induced phase transition. While they have recently attracted attention as potential highly efficient molecular actuators,less than two dozens of thermosalient molecular crystals have been reported to date,a nd the design of such molecules as well as how they assemble to express at hermosalient effect are unknown. Herein, we demonstrate how the cooperative molecular motion of twisted p units could serve to develop at hermo-responsive jumping molecular crystal with ah ydrogen-bonded organic framework (HOF) of tetra-[2,3]thienylene tetracarboxylic acid (1). The cooperative change in the molecular structure triggered by the desolvation of THF in the channel of the HOF structure induced not only ac hangei nt he structure of HOF but also mechanical force. Hydrogen bonding interactions contributed significant thermal stability to maintain the HOF assembly even with ad ynamic structural change.

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“…[11] We report herein that when excited with strong cw UV light, micrometer-to millimeter-sized prismatic crystals of [Co(NH 3 ) 5 (NO 2 )]Cl(NO 3 ) (1-N) suddenly hop off the surface and travel up to several tens of centimeters, that is, 10 2 -10 5 times their own length ( Figure 1). By analogy to the respective thermally induced jumping, [12][13][14][15][16][17][18][19][20][21][22][23] we suggest the term "photosalient effect" for this photomechanical phenomenon. The effect is not intuitively expected for a simple inorganic compound with a discrete ionic structure such as 1-N, and it represents the visually most impressive macroscopic manifestation of the stress that can develop in response to the mechanical force created inside a crystal as a result of miniscule structure perturbation, by sudden release of the collective energy through the concerted action of the intermolecular interactions at the molecular level.…”

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confidence: 99%

Dynamic Single Crystals: Kinematic Analysis of Photoinduced Crystal Jumping (The Photosalient Effect)

et al. 2013

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Crystals on the move: If they are subjected to a strong light stimulus, crystals of the cobalt coordination compound [Co(NH3)5(NO2)]Cl(NO3) undergo sudden jumps and leap over distances 10(2)-10(5) times their own size to release the strain that accumulates in their interior. The first quantitative kinematic analysis of this phenomenon is reported. The observed effect could be employed for actuation on the macroscopic scale.

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A crystal that hops in phase transition, the structure of trans,trans,anti,trans,trans-perhydropyrene

Cited by 39 publications

References 1 publication

Dual Stress and Thermally Driven Mechanical Properties of the Same Organic Crystal: 2,6-Dichlorobenzylidene-4-fluoro-3-nitroaniline

Dual Stress and Thermally Driven Mechanical Properties of the Same Organic Crystal: 2,6-Dichlorobenzylidene-4-fluoro-3-nitroaniline

Jumping Crystal of a Hydrogen‐Bonded Organic Framework Induced by the Collective Molecular Motion of a Twisted π System

Dynamic Single Crystals: Kinematic Analysis of Photoinduced Crystal Jumping (The Photosalient Effect)

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