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The realization of above room-temperature ferromagnetism in the two-dimensional (2D) magnet Fe 5 GeTe 2 represents a major advance for the use of van der Waals (vdW) materials in practical spintronic applications. In particular, observations of magnetic skyrmions and related states within exfoliated flakes of this material provide a pathway to the fine-tuning of topological spin textures via 2D material heterostructure engineering. However, there are conflicting reports as to the nature of the magnetic structures in Fe 5 GeTe 2 . The matter is further complicated by the study of two types of Fe 5 GeTe 2 crystals with markedly different structural and magnetic properties, distinguished by their specific fabrication procedure: whether they are slowly cooled or rapidly quenched from the growth temperature. In this work, we combine X-ray and electron microscopy to observe the formation of magnetic stripe domains, skyrmion-like type-I, and topologically trivial type-II bubbles, within exfoliated flakes of Fe 5 GeTe 2 . The results reveal the influence of the magnetic ordering of the Fe1 sublattice below 150 K, which dramatically alters the magnetocrystalline anisotropy and leads to a complex magnetic phase diagram and a sudden change of the stability of the magnetic textures. In addition, we highlight the significant differences in the magnetic structures intrinsic to slow-cooled and quenched Fe 5 GeTe 2 flakes.

Covalent organic frameworks (COFs) are a class of porous materials whose sorption properties have so far been studied primarily by physisorption. Quantifying the self-diffusion of guest molecules inside their nanometer-sized pores allows for a better understanding of confinement effects or transport limitations and is thus essential for various applications ranging from molecular separation to catalysis. Using a combination of pulsed field gradient nuclear magnetic resonance measurements and molecular dynamics simulations, we have studied the self-diffusion of acetonitrile and chloroform in the 1D pore channels of two imine-linked COFs (PI-3-COF) with different levels of crystallinity and porosity. The higher crystallinity and porosity sample exhibited anisotropic diffusion for MeCN parallel to the pore direction, with a diffusion coefficient of D par = 6.1(3) × 10 -10 m 2 s -1 at 300 K, indicating 1D transport and a 7.4-fold reduction in self-diffusion compared to the bulk liquid. This finding aligns with molecular dynamics simulations predicting 5.4-fold reduction, assuming an offset-stacked COF layer arrangement. In the low-porosity sample, more frequent diffusion barriers result in isotropic, yet significantly reduced diffusivities ( D B = 1.4(1) × 10 -11 m 2 s -1 ). Diffusion coefficients for chloroform at 300 K in the pores of the high- ( D par = 1.1(2) × 10 -10 m 2 s -1 ) and low-porosity ( D B = 4.5(1) × 10 -12 m 2 s -1 ) samples reproduce these trends. Our multimodal study thus highlights the significant influence of real structure effects such as stacking faults and grain boundaries on the long-range diffusivity of molecular guest species while suggesting efficient intracrystalline transport at short diffusion times.

Two-dimensional van der Waals (vdW) heterostructures are an attractive platform for studying exchange bias due to their defect-free and atomically flat interfaces. Chromium thiophosphate (CrPS 4 ), an antiferromagnetic material, possesses uncompensated magnetic spins in a single layer, rendering it a promising candidate for exploring exchange bias phenomena. Recent findings have highlighted that naturally oxidized vdW ferromagnetic Fe 3 GeTe 2 exhibits exchange bias, attributed to the antiferromagnetic coupling of its ultrathin surface oxide layer (O-FGT) with the underlying unoxidized Fe 3 GeTe 2 . Anomalous Hall measurements are employed to scrutinize the exchange bias within the CrPS 4 /(O-FGT)/Fe 3 GeTe 2 heterostructure. This analysis takes into account the contributions from both the perfectly uncompensated interfacial CrPS 4 layer and the interfacial oxide layer. Intriguingly, a distinct and nonmonotonic exchange bias trend is observed as a function of temperature below 140 K. The occurrence of exchange bias induced by a "preset field" implies that the prevailing phase in the polycrystalline surface oxide is ferrimagnetic Fe 3 O 4 . Moreover, the exchange bias induced by the ferrimagnetic Fe 3 O 4 is significantly modulated by the presence of the van der Waals antiferromagnetic CrPS 4 layer, forming a heterostructure, along with additional iron oxide phases within the oxide layer. These findings underscore the intricate and complex nature of exchange bias in van der Waals heterostructures, highlighting their potential for tailored manipulation and control.

The reversible formation of hydrogen bonds is a ubiquitous mechanism for controlling molecular assembly in biological systems. However, achieving predictable reversibility in artificial two-dimensional (2D) materials remains a significant challenge. Here, we use an external electric field (EEF) at the solid/liquid interface to trigger the switching of H-bond-linked 2D networks using a scanning tunneling microscope. Assisted by density functional theory and molecular dynamics simulations, we systematically vary the molecule-to-molecule interactions, i.e., the hydrogen-bonding strength, as well as the molecule-to-substrate interactions to analyze the EEF switching effect. By tuning the building block's hydrogen-bonding ability (carboxylic acids vs aldehydes) and substrate nature and charge (graphite, graphene/Cu, graphene/SiO 2 ), we induce or freeze the switching properties and control the final polymorphic output in the 2D network. Our results indicate that the switching ability is not inherent to any particular building block but instead relies on a synergistic combination of the relative adsorbate/adsorbate and absorbate/substrate energetic contributions under surface polarization. Furthermore, we describe the dynamics of the switching mechanism based on the rotation of carboxylic groups and proton exchange, which generate the polarizable species that are influenced by the EEF. This work provides insights into the design and control of reversible molecular assembly in 2D materials, with potential applications in a wide range of fields, including sensors and electronics.

The preparation of wavelength-specific Bragg mirrors was realized by an effective and reproducible spin-coating approach using colloidal suspensions of functionalized mesoporous silica nanoparticles and titania sols. Due to the small particle size and the resulting low surface roughness, the formation of multilayers was possible without transmitting defects on the surface with every following coating step. The Bragg reflectors show sensitivity toward specific relative pressures of organic vapors such as toluene, giving rise to optically encoded adsorption properties as a function of solvent pressure and, thus, to optical adsorption isotherms.

Clays have shown potential as intelligent optical sensing platforms when integrated into a one-dimensional photonic crystal (PC) environment. The clay component imparts intrinsic functionality to the multilayer system by combining the signature ion exchange with the tunable structural color of photonic crystals, giving rise to environmentally sensitive photonic clay architectures. We have fabricated different Laponite-based 1D PCs and clay defect PCs by simple bottom-up self-assembly methodologies and elaborate their working principles and chemically encoded optical response. Accessibility of the multilayer system to analytes is studied on the background of the barrier properties of clays and diffusion control by the mesoporous oxide layers. The time dependence of analyte uptake and the extent and driving force for analyte release are pointed out and discussed in the context of different interactions between the clay layers and analytes. We demonstrate the possibility of optical cycling associated with repeated analyte uptake and removal processes, rendering photonic clays recyclable and low cost sensing platforms with simple optical read-out.