<p>Chemical functionalization has demonstrated to be a powerful approach to tailor the physical and chemical properties of two-dimensional (2D) materials, to increase their processability and</p> <p>stability, to add new functionalities and, even, to create new 2D materials. However, this post synthetic method – which involves the anchoring of molecules on the surface of an exfoliated 2D crystal – inevitably leads to defective materials, which lack long-range structural order. If defect-free functionalized monolayers are required, a radically new approach needs to be developed. Here we present a pre-synthetic method based on coordination chemistry that affords the isolation of crystalline functionalized monolayers. This involves functionalization of the ligand prior to the formation of the 2D material. The concept is illustrated using layered coordination polymers formed by reacting various benzimidazole derivatives with ferrocene. This surface tuneability, together with the robust magnetic and mechanical properties of these 2D materials, make them exceptional candidates for studying the magnetism in the 2D limit, as well as for developing membranes for selective molecular sensing.</p>

Layered double hydroxides (LDHs) are ac lass of 2D anionic materials exhibiting wide chemical versatility and promising applications in different fields, ranging from catalysis to energy storage and conversion.H owever,t he covalent chemistry of this kind of 2D materials is still barely explored. Herein, the covalentf unctionalization with silanes of am agnetic NiFe-LDH is reported. The synthetic route consists of at opochemical approach followed by anion exchange reaction with surfactant molecules prior to covalent functionalization with the (3-aminopropyl)triethoxysilane (APTES) molecules. The functionalized NiFe-APTES was fully characterized by X-ray diffraction, infrared spectroscopy, electron microscopy,t hermogravimetric analysis coupled with mass spectrometry and 29 Si solid-state nuclear magnetic resonance, among others. The effect on the electronic properties of the functionalizedL DH was investigated by am agnetic study in combination with Mçssbauer spectroscopy. Moreover,t he reversibility of the silane-functionalizationa t basic pH was demonstrated, and the quality of the resulting LDH was proven by studying the electrochemical performance in the oxygen evolution reaction in basic media. Furthermore, the anion exchange capability for the NiFe-APTES was tested employing Cr VI ,r esulting in an increase of 200 %o ft he anion retention. This report allows for an ew degree of tunability of LDHs, openingt he door to the synthesis of new hybrid architectures and materials.[a] Dr.Figure 2. FESEM (A), TEM (B) and mapping images (bottom panel) of NiFe-APTES. The inset in (A) shows DLS and the inset in (B) showst he SAED pattern. Mapping imagesare obtained from the single particle in the bottom left image( scale bar of 100 nm).

A bifunctionalized polyoxometalate (POM), [V6O19(C16H15N6O)2]2-, which contains a redox active hexavanadate moiety covalently linked to two tridentate 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) ligands, has been prepared and characterized. Reaction of this hybrid molecule...

The design of efficient food contact materials that maintain optimal levels of food safety is of paramount relevance to reduce the increasing foodborne illnesses. In this work, we develop a smart composite MOF-based material that fosters a unique prolonged antibacterial activity. The composite is obtained by entrapping a natural preserving food molecule, carvacrol, into the mesoporous MIL-100(Fe) material following a direct and biocompatible impregnation method and obtaining particularly high payloads. By exploiting the intrinsic redox nature of MIL-100(Fe) material it is possible to achieve a prolonged activity against E. coli bacteria due to a triggered two-step carvacrol release of films containing the carvacrol@MOF composite. Essentially, it was discovered that based on the underlying chemical interaction among MIL-100(Fe) and carvacrol, it is possible to undergo a reversible charge transfer process between the metallic MOF counterpart and the carvacrol upon certain physical stimuli. During this process, the preferred carvacrol binding site has been monitored by IR, Mössbauer and EPR spectroscopies and is supported by theoretical calculations.

The design of efficient food contact materials that maintain optimal levels of food safety is of paramount relevance to reduce the increasing foodborne illnesses. In this work, we develop a smart composite MOF-based material that fosters a unique prolonged antibacterial activity. The composite is obtained by entrapping a natural preserving food molecule, carvacrol, into the mesoporous MIL-100(Fe) material following a direct and biocompatible impregnation method and obtaining particularly high payloads. By exploiting the intrinsic redox nature of MIL-100(Fe) material it is possible to achieve a prolonged activity against E. coli bacteria due to a triggered two-step carvacrol release of films containing the carvacrol@MOF composite. Essentially, it was discovered that based on the underlying chemical interaction among MIL-100(Fe) and carvacrol, it is possible to undergo a reversible charge transfer process between the metallic MOF counterpart and the carvacrol upon certain physical stimuli. During this process, the preferred carvacrol binding site has been monitored by IR, Mössbauer and EPR spectroscopies and is supported by theoretical calculations.