Elucidating 2D Charge-Density-Wave Atomic Structure in an MX-Chain by the 3D-ΔPair Distribution Function Method.

The front cover artwork is provided by Prof. Masahiro Yamashita's group at Tohoku University and designed by Dr. Laurent Guérin at University of Rennes 1. The image illustrates that the atomic structure of a 2D charge density wave can be revealed although the planes associated to this local 2D order are randomly stacked preventing the use of conventional structure determination techniques. Read the full text of the Research Article at 10.1002/cphc.202100857.

Elucidating 2D Charge-Density-Wave Atomic Structure in an MX-Chain by the 3D-ΔPair Distribution Function Method.

Many solids, particularly low-dimensional systems, exhibit charge density waves (CDWs). In one dimension, charge density waves are well understood, but in two dimensions, their structure and their origin are difficult to reveal. Herein, the 2D charge-density-wave atomic structure and stabilization mechanism in the bromide-bridged Pd compound [Pd(cptn)2 Br]Br2 (cptn=1R,2R-diaminocyclopentane) is investigated by means of single-crystal X-ray diffraction employing the 3D-Δpair distribution function (3D-ΔPDF) method. Analysis of the diffuse scattering using 3D-ΔPDF shows that a 2D-CDW is stabilized by a hydrogen-bonding network between Br- counteranion and the amine (NH2 ) group of the cptn in-plane ligand, and that 3D ordering is prevented due to a weak plane to plane correlation. We extract the effective displacements of the atoms describing the atomic structure quantitatively and discuss the stabilization mechanism of the 2D-CDW. Our study provides a method to identify and measure the key interaction responsible for the dimensionality and stability of the CDW that can help further progress of rational design.

The creation of modulated monoclinic aperiodic composites in n-alkane/urea compounds.

n-Dodecane/urea is a member of the prototype series of n-alkane/urea inclusion compounds. At room temperature, it presents a quasi-one dimensional liquid-like state for the confined guest molecules within the rigid, hexagonal framework of the urea host. At lower temperatures, we report the existence of two other phases. Below Tc=248 K there appears a phase with rank four superspace group P6122(00γ), the one typically observed at room temperature in n-alkane/urea compounds with longer guest molecules. A misfit parameter, defined by the ratio γ=ch /cg (chost/cguest), is found to be 0.632±0.005. Below Tc1=123 K, a monoclinic modulated phase is created with a constant shift along c of the guest molecules in adjacent channels. The maximal monoclinic space group for this structure is P1211(α0γ). Analogies and differences with n-heptane/urea, which also presents a monoclinic, modulated low-temperature phase, are discussed.

Long-range modulation of a composite crystal in a five-dimensional superspace.

The intergrowth crystal of n-tetracosane/urea presents a misfit parameter, defined by the ratio γ = ch /cg (chost/cguest), that is very close to a commensurate value (γ ≅ 1/3). High-resolution diffraction studies presented here reveal an aperiodic misfit parameter of γ = 0.3369, which is found to be constant at all temperatures studied. A complex sequence of structural phases is reported. The high temperature phase (phase I) exists in the four-dimensional superspace group P6122(00γ). At Tc1 = 179(1) K, a ferroelastic phase transition increases the dimension of the crystallographic superspace. This orthorhombic phase (phase II) is characterized by the five-dimensional (5D) superspace group C2221(00γ)(10δ) with a modulation vector ao* + cm* = ao* + δ · ch*, in which the supplementary misfit parameter is δ = 0.025(1) in host reciprocal units. This corresponds to the appearance of a modulation of very long period (about 440 ± 16 Å). At Tc2 = 163.0(5) K, a 5D to 5D phase transition leads to the crystallographic superspace group P212121(00γ)(00δ) with a very similar value of δ. This phase transition reveals a significant hysteresis effect.

Hidden degrees of freedom in aperiodic materials.

Numerous crystalline materials, including those of bioorganic origin, comprise incommensurate sublattices whose mutual arrangement is described in a superspace framework exceeding three dimensions. We report direct observation by neutron diffraction of superspace symmetry breaking in a solid-solid phase transition of an incommensurate host-guest system: the channel inclusion compound of nonadecane/urea. Strikingly, this phase transition generates a unit cell doubling that concerns only the modulation of one substructure by the other-an internal variable available only in superspace. This unanticipated pathway for degrees of freedom to rearrange leads to a second phase transition, which again is controlled by the higher dimensionality of superspace. These results reveal nature's capacity to explore the increased number of phases allowed in aperiodic crystals.

Interactions in self-organized nanoporous organic crystals.

This Letter reports on the structural analysis of a self-assembly material, the prototype host-guest urea-alkane nanoporous crystal. Different spectroscopic techniques, under hydrostatic pressure, reveal a totally unexpected ordered phase where ordering does not require any apparent deformation of the host. This fundamental observation raises the question of the actual interactions in other similar supramolecular or biological tubular systems.

First one-dimensional stress-strain experiments inside an aperiodic inclusion compound: evidence of depinning effects.

This Letter reports on the first observation of depinning under hydrostatic pressure of the guest and host sublattices inside the aperiodic nonadecane-urea inclusion compound. This leads to a unique way for a direct determination of the one-dimensional interguest interaction (1 N/m for nonadecane).