2018
DOI: 10.1002/ange.201806431
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Elastically Flexible Crystals have Disparate Mechanisms of Molecular Movement Induced by Strain and Heat

Abstract: Elastically flexible crystals form an emerging class of materials that exhibit a range of notable properties. The mechanism of thermal expansion in flexible crystals of bis(acetylacetonato)copper(II) is compared with the mechanism of molecular motion induced by bending and it is demonstrated that the two mechanisms are distinct. Upon bending, individual molecules within the crystal structure reversibly rotate, while thermal expansion results predominantly in an increase in intermolecular separations with only … Show more

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Cited by 17 publications
(8 citation statements)
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“…There is no change in the hydrogen bond, nor any other bond lengths within the molecules. While similar to the mechanism reported for [Cu(acac) 2 ], 3,7 the changing separation of the π-stacked molecules and the symmetry of 1 distinguish this new mechanism as the molecular rotations in this case are bidirectional.…”
supporting
confidence: 79%
“…There is no change in the hydrogen bond, nor any other bond lengths within the molecules. While similar to the mechanism reported for [Cu(acac) 2 ], 3,7 the changing separation of the π-stacked molecules and the symmetry of 1 distinguish this new mechanism as the molecular rotations in this case are bidirectional.…”
supporting
confidence: 79%
“…While N,O chelation would seem to be a possible mode of coordination for L3, it is clearly not favoured over O,O chelation (of the diketonate form), an interaction which appears to inhibit any N -coordination and thus polymerization, as shown by the presence of molecular bis(diketonate) species in the crystal structures of the isolated complex. In contrast to the previously reported Cu complex with phenyl substituted linker, [ 34 ] C1 crystallizes in two distinct polymorphic forms, triclinic P-1 (tC1) and monoclinic P2 1 /n (mC1), in both of which the complex has a distorted square planar geometry around the copper centre with two anionic O,O’ -chelates from β -diketonate moieties coordinated in a trans planar fashion ( Figure 7 a) [ 38 ] There are only very minor differences between the polymorphs ( Figure 7 b). The Cu–O distances are 1.904–1.907 Å and 1.914–1.917 Å for tC1 and mC1, respectively.…”
Section: Resultsmentioning
confidence: 71%
“…It has recently been shown on single crystals of elastically flexible copper(II) acetylacetonate that the molecular motions responsible for thermal expansion and bending are different. 22 , 23 Therefore, a reliable description of the thermoelastic response of such materials requires the simultaneous description of structural changes induced by thermal expansion and strain. A successful prediction relies on the balanced description of the interplay of these effects.…”
mentioning
confidence: 99%
“…We apply our scheme to the investigation of the thermoelasticity of the stimuli-responsive, metal–organic copper(II) acetylacetonate crystal: a system that has recently attracted a lot of attention because of its unusual high flexibility 22 and its different structural mechanisms induced by temperature and strain. 23 Present quantum-mechanical calculations allow to report the first complete characterization of the 3D anisotropic elastic response of this system, as well as its thermal evolution. Inclusion of thermal effects up to room temperature results in dramatic changes of the statically computed values.…”
mentioning
confidence: 99%