One‐Dimensional Materials Supported in Two‐Dimensional Van der Waals Metal–Organic Frameworks with Optical Anisotropy Switching via Twist‐Engineering

Van der Waals (vdW) materials provide a platform to study and control the physical properties of low-dimensional materials. While strategies developed for 2D crystals are not directly transferable to 1D systems, we can benefit from them by creating layers formed by interconnected chains. Here, we develop a molecular strategy to illustrate this concept consisting of assembling 1D materials in 2D metal-organic frameworks (MOFs). Crystals of [FeX(pzX)(bpy)] (X = Cl, F; pz = pyrazole; bpy = bipyridine) consist of iron chains along the b-axis, crosslinked via bpy ligands along the a-axis to form 2D layers, stacked along the c-axis via vdW forces. This structural anisotropy manifests itself in highly-anisotropic optical properties, as demonstrated by optical measurements in the visible and terahertz ranges, results which are supported by DFT calculations. Chemical substitution enables the tuning of the optical properties, as exemplified by the photoluminescence of the Cl-derivative, which is quenched for the F-derivative. Thin-layers are obtained by mechanical exfoliation, and their optical properties are further tuned through the fabrication of orthogonally-twisted vdW heterostructures, enabling to effectively switch-off the optical anisotropy. Our work highlights the chemical flexibility of vdW layered MOFs as a platform for designing and manipulating 1D architectures.