arXiv · 1706.01121
Incommensurate chirality density wave transition in a hybrid molecular framework
Abstract
Using single-crystal X-ray diffraction we characterise the 235\,K incommensurate phase transition in the hybrid molecular framework tetraethylammonium silver(I) dicyanoargentate, [NEt$_4$]Ag$_3$(CN)$_4$. We demonstrate the transition to involve spontaneous resolution of chiral [NEt$_4$]$^+$ conformations, giving rise to a state in which molecular chirality is incommensurately modulated throughout the crystal lattice. We refer to this state as an incommensurate chirality density wave (XDW) phase, which represents a fundamentally new type of chiral symmetry breaking in the solid state. Drawing on parallels to the incommensurate ferroelectric transition of NaNO$_2$ we suggest the XDW state arises through coupling between acoustic (shear) and molecular rotoinversion modes. Such coupling is symmetry-forbidden at the Brillouin zone centre but symmetry-allowed for small but finite modulation vectors $\mathbf q=[0,0,q_z]^\ast$. The importance of long-wavelength chirality modulations in the physics of this hybrid framework may have implications for the generation of mesoscale chiral textures, as required for advanced photonic materials.
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Joshua A. Hill, Kirsten E. Christensen, Andrew L. Goodwin. 2017-06-04. Incommensurate chirality density wave transition in a hybrid molecular framework. https://doi.org/10.1103/physrevlett.119.115501
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