Manipulating properties of matter at the nanoscale is the essence of nanotechnology, which has enabled the realization of quantum dots, nanotubes, metamaterials, and two-dimensional materials with tailored electronic and optical properties. Two-dimensional semiconductors have revealed promising perspectives in nanotechnology. However, the tunability of their physical properties is challenging for semiconductors studied until now. Here we show the ability of morphological manipulation strategies, such as nanotexturing or, at the limit, important surface roughness, to enhance light absorption and the luminescent response of atomically thin indium selenide nanosheets. Besides, quantum-size confinement effects make this two-dimensional semiconductor to exhibit one of the largest band gap tunability ranges observed in a two-dimensional semiconductor: from infrared, in bulk material, to visible wavelengths, at the single layer. These results are relevant for the design of new optoelectronic devices, including heterostructures of two-dimensional materials with optimized band gap functionalities and in-plane heterojunctions with minimal junction defect density.
The last decade has witnessed a great activity in the realm of porous coordination polymers (PCPs). Their extreme chemical versatility and porosity has allowed chemists to consider PCPs as a new class of functional materials that are able to mimic, and even improve, the functions of zeolites, for example, storage, separation, and heterogeneous catalysis. [1] Furthermore, implementation of PCPs with solid-state properties (optical, magnetic, charge transport, etc.) would enable the expression of host-guest interactions in sorption and desorption processes in a sensory way as a response of the framework producing drastic physicochemical changes at ordinary temperatures. This almost unexplored strategy could provide a new generation of PCP-based sensors.[2]The chemo-responsive behavior of the Hofmann clathratePd, [3a] Pt [3a] ) based on the spin-crossover properties of the Fe II joints was recently demonstrated. The cooperative response mediated by the components of the framework confers bistable behavior to the solid at room temperature. These PCPs form a 3D pillared-layer-type porous framework consisting of cyano-bridged Fe II M II layers and pz pillar ligands, and adsorb various guest molecules. A bimodal reversible change of spin state at the Fe II sites was observed concomitantly with the uptake of guest molecules switching between the high-spin state (HS, yellow), stabilized by hydroxylic solvents and five-and six-membered aromatic molecules, and the low-spin state (LS, red-brown), stabilized by CS 2 (for M = Pt) [3a] or CH 3 CN (for M = Ni) [3b] at 298 K. In the framework, guest molecules can interact with the pyrazine pillar ligands (site A) and the M II centers (site B). One important feature not yet explored in these PCPs is the coordinative unsaturation of the M II centers. Incorporation of coordinatively unsaturated metal centers, so-called "open metal sites", may enhance the adsorptive selectivity for particular guest substances.[4] Herein we report the chemisorptive uptake of dihalogen molecules involving associative oxidation of Pt II to Pt IV and reduction of the dihalogen to the corresponding halide to give {Fe(pz) [Pt(CN)
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