Hingeless Negative Linear Compression in the Mechanochromic Gold Complex [(C6F5Au)2(μ‐1,4‐diisocyanobenzene)]

Woodall, Christopher H.; Beavers, Christine M.; Christensen, Jeppe; Hatcher, Lauren E.; Intissar, Mourad; Parlett, Andrew; Teat, Simon J.; Reber, Christian; Raithby, Paul R.

doi:10.1002/anie.201302825

Cited by 59 publications

(51 citation statements)

References 38 publications

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“…anharmonicity. We anticipate that the discovery of anomalous mechanics in increasingly many systems based on vdW-type interactions [66,67] will motivate further research effort along precisely these lines.…”

Section: Discussionmentioning

confidence: 99%

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Sapnik

Liu

Boström

et al. 2018

Journal of Solid State Chemistry

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We report the synthesis and structural characterisation of the molecular framework copper(I) hexacyanocobaltate(III), Cu 3 [Co(CN) 6 ], which we find to be isostructural to H 3 [Co(CN) 6 ] and the colossal negative thermal expansion material Ag 3 [Co(CN) 6 ]. Using synchrotron X-ray powder diffraction measurements, we find strong positive and negative thermal expansion behaviour respectively perpendicular and parallel to the trigonal crystal axis: α = 25.4(5) MK . These opposing effects collectively result in a volume expansivity α = 7.4(11) MK V −1 that is remarkably small for an anisotropic molecular framework. This thermal response is discussed in the context of the behaviour of the analogous H-and Ag-containing systems. We make use of density-functional theory with many-body dispersion interactions (DFT + MBD) to demonstrate that Cu + …Cu + metallophilic ('cuprophilic') interactions are significantly weaker in Cu 3 [Co(CN) 6 ] than Ag + …Ag + interactions in Ag 3 [Co(CN) 6 ], but that this lowering of energy scale counterintuitively translates to a more moderate-rather than enhanced-degree of structural flexibility. The same conclusion is drawn from consideration of a simple GULP model, which we also present here. Our results demonstrate that strong interactions can actually be exploited in the design of ultra-responsive materials if those interactions are set up to act in tension.

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Section: Discussionmentioning

confidence: 99%

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Sapnik

Liu

Boström

et al. 2018

Journal of Solid State Chemistry

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“…In our case, it involves intramolecular interaction changes, whereas the others are based on intermolecular ones involving excimers 23 and intermolecular Au−Au interactions. 24 …”

Section: Inorganic Chemistrymentioning

confidence: 99%

“…23,24 In those cases, the effect of hydrostatic pressure on the luminescence properties appeared to be different from that of manual grinding; thus, only indirect information into the mechanochromism mechanism could have been obtained. 23,24 In this context, the study of mechanochromic compounds that exhibit similar behavior under both hydrostatic pressure and grinding is particularly attractive.The molecular copper iodide cubane clusters [Cu 4 I 4 L 4 ] (L = phosphine ligand) constitute an original family of luminescent mechanochromic compounds exhibiting a great change of the luminescence properties upon grinding. 25−28 The metallic interactions are highly suspected to be involved in the mechanochromism mechanism.…”

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confidence: 98%

Pressure Control of Cuprophilic Interactions in a Luminescent Mechanochromic Copper Cluster

et al. 2015

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For the development of applications based on mechanochromic luminescent materials, a comprehensive study of the mechanism responsible for the emission changes is required. We report the study of a mechanochromic copper iodide cluster under hydrostatic pressure, which allows control of crystal packing via modification of the intermolecular interactions. In situ single-crystal powder X-ray diffraction analysis and emission measurements under pressure permit one to establish a direct correlation between the molecular structure and luminescence properties and, in particular, to demonstrate that cuprophilic interactions are responsible for the stimuli-responsive luminescence properties of such multinuclear coordination compounds.

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“…Suggested applications for NLC compounds include as sensors, actuators, artificial muscles and as components of advanced structural materials. One system that gives rise to negative linear compressibility (NLC) is the linear organoauric complex (Figure 28), which does so despite there being no formal bond about the "hinge" (Figure 29), the complex crystallising as alternating sheets that give rise to a 'wine rack' motif when viewed down the c axis [49]. Upon the application of pressure the angle about the pivot, measured as the torsion angle NC−Au···Au−CN, closes from 74.314 (9) …”

Section: Complexes Exhibiting Negative Linear Compressibilitymentioning

confidence: 99%

Structural chemistry of metal coordination complexes at high pressure

Tidey

Wong

Schröder

et al. 2014

Coordination Chemistry Reviews

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The application of pressures of up to about 10 GPa may induce significant geometric, configurational, conformational and packing changes in molecular solids. This review highlights and describes recent advances in high pressure studies of coordination complexes, many of which have been conducted at synchrotrons or other central facilities. The main focus is on the wide range of geometric changes which occur with pressure. In some cases these changes have associated physical effects, and the review describes materials exhibiting negative linear compressibility, spin cross-over phenomena, magnetism and molecular conduction, as well as detailing the exciting possibilities for future developments in this area of research.

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Hingeless Negative Linear Compression in the Mechanochromic Gold Complex [(C₆F₅Au)₂(μ‐1,4‐diisocyanobenzene)]

Cited by 59 publications

References 38 publications

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6]

Pressure Control of Cuprophilic Interactions in a Luminescent Mechanochromic Copper Cluster

Structural chemistry of metal coordination complexes at high pressure

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