A fluorinated 2D magnetic coordination polymer

Herein we show the versatility of coordination chemistry to design and expand a family of 2D materials by incorporating F groups at the surface of the layers. Through the use of a prefuntionalized organic linker with F groups, it is possible to achieve a layered magnetic material based on Fe(II) centers that are chemically stable in open air, contrary to the known 2D inorganic magnetic materials. The high quality of the single crystals and their robustness allow to fabricate 2D molecular materials by micromechanical exfoliation, preserving the crystalline nature of these layers together with the desired functionalization

Chemical Design and Magnetic Ordering in Thin Layers of 2D Metal−Organic Frameworks (MOFs)

Through rational chemical design, and thanks to the hybrid nature of metal-organic frameworks (MOFs), it is possible to prepare molecule-based 2D magnetic materials stable at ambient conditions. Here, we illustrate the versatility of this approach by changing both the metallic nodes and the ligands in a family of layered MOFs that allows the tuning of their magnetic properties. Specifically, the reaction of benzimidazole-type ligands with different metal centers (MII = Fe, Co, Mn, Zn) in a solvent-free synthesis produces a family of crystalline materials, denoted as MUV-1(M), which order antiferromagnetically with critical temperatures that depend on M. Furthermore, the incorporation of additional substituents in the ligand results in a novel system, denoted as MUV-8, formed by covalently bound magnetic double layers interconnected by van der Waals interactions, a topology that is very rare in the field of 2D materials and unprecedented for 2D magnets. These layered materials are robust enough to be mechanically exfoliated down to a few layers with large lateral dimensions. Finally, the robustness and crystallinity of these layered MOFs allow the fabrication of nanomechanical resonators that can be used to detect─through laser interferometry─the magnetic order in thin layers of these 2D molecule-based antiferromagnets

Electronic, Structural and Functional Versatility in Tetrathiafulvalene-Lanthanide Metal-Organic Frameworks

Tetrathiafulvalene-lanthanide (TTF-Ln) metal-organic frameworks (MOFs) are an interesting class of multifunctional materials in which porosity can be combined with electronic properties such as electrical conductivity, redox activity, luminescence and magnetism. Herein a new family of isostructural TTF-Ln MOFs is reported, denoted as MUV-5(Ln) (Ln=Gd, Tb, Dy, Ho, Er), exhibiting semiconducting properties as a consequence of the short intermolecular S⋅⋅⋅S contacts established along the chain direction between partially oxidised TTF moieties. In addition, this family shows photoluminescence properties and single-molecule magnetic behaviour, finding near-infrared (NIR) photoluminescence in the Yb/Er derivative and slow relaxation of the magnetisation in the Dy and Er derivatives. As such properties are dependent on the electronic structure of the lanthanide ion, the immense structural, electronic and functional versatility of this class of materials is emphasised

Transgenic Mouse Models of Alzheimer’s Disease: An Integrative Analysis

Alzheimer’s disease (AD) constitutes the most prominent form of dementia among elderly individuals worldwide. Disease modeling using murine transgenic mice was first initiated thanks to the discovery of heritable mutations in amyloid precursor protein (APP) and presenilins (PS) genes. However, due to the repeated failure of translational applications from animal models to human patients, along with the recent advances in genetic susceptibility and our current understanding on disease biology, these models have evolved over time in an attempt to better reproduce the complexity of this devastating disease and improve their applicability. In this review, we provide a comprehensive overview about the major pathological elements of human AD (plaques, tauopathy, synaptic damage, neuronal death, neuroinflammation and glial dysfunction), discussing the knowledge that available mouse models have provided about the mechanisms underlying human disease. Moreover, we highlight the pros and cons of current models, and the revolution offered by the concomitant use of transgenic mice and omics technologies that may lead to a more rapid improvement of the present modeling batterThis research was funded by INSTITUTO DE SALUD CARLOS III (ISCiii) of Spain, cofinanced by FEDER funds from European Union, through grants PI21/00915 (to AG) and PI21/00914 (to JV); by JUNTA DE ANDALUCIA CONSEJERÍA DE ECONOMÍA Y CONOCIMIENTO through grants UMA18-FEDERJA-211 (to AG), UMA20-FEDERJA-104 (to IMG), P18-RT-2233 (to AG) and US-1262734 (to JV) co-financed by Programa Operativo FEDER 2014–2020 and CONSEJERIA DE SALUD grant PI-0276-2018 (to JAGL); by SPANISH MINISTER OF SCIENCE AND INNOVATION grant PID2019-108911RA-100 (to DBV), BEATRIZ GALINDO PROGRAM BAGAL18/00052 (to DBV), Alzheimer Association AARG-22-928219 (to DBV), grant PID2019-107090RA-100 (to IMG) and RAMON Y CAJAL PROGRAM RYC-2017-21879 (to IMG); and by MALAGA UNIVERSITY grant B1-2019_07 (to ESM), grant B1-2020_04 (to JAGL), grant B1-2019_06 (to IMG) and NASARD grant 27565 2018 (to IMG). M.M.-O. held a predoctoral contract from Malaga University, J.J.F.-V. held a postdoctoral contract from Malaga University, and E.S.-M. a postdoctoral contract (DOC_00251) from Junta de Andalucia. Partial funding for open access charge: Universidad de Málaga

A fluorinated 2D magnetic coordination polymer

Herein we show the versatility of coordination chemistry to design and expand a family of 2D materials by incorporating F groups at the surface of the layers. Through of use of a prefuntionalized organic linker with F groups, it is possible to achieve a layered magnetic material based on Fe(II) centers that are chemically stable in open air, contrary to the known 2D inorganic magnetic materials. The high quality of the single crystals and their robustness allow to fabricate 2D molecular materials by micromechanical exfoliation, preserving the crystalline nature of these layers together with the desired functionalization

A fluorinated 2D magnetic coordination polymer

Herein we show the versatility of coordination chemistry to design and expand a family of 2D materials by incorporating F groups at the surface of the layers. Through the use of a prefuntionalized organic linker with F groups, it is possible to achieve a layered magnetic material based on Fe(ii) centers that are chemically stable in open air, contrary to the known 2D inorganic magnetic materials. The high quality of the single crystals and their robustness allow to fabricate 2D molecular materials by micromechanical exfoliation, preserving the crystalline nature of these layers together with the desired functionalization.This work has been supported by the EU (ERC Advanced Grant MOL-2D 788222 and ERC Consolidator Grant S-CAGE 724681), grants PID2020-117177GB-I00, PID2020-117152RB-I00 and CEX2019-000919-M, funded by MCIN/AEI/10.13039/501100011033, and the Generalitat Valenciana (PROMETEO program, IDIFEDER/2018/061 and iDiFEDER/2020/063). J. L.-C. acknowledges the Universitat de València for an “Atracció de Talent” fellowship

Multivariate sodalite Zeolitic Imidazolate frameworks: a direct solvent-free synthesis

Different mixed-ligand Zeolitic Imidazolate Frameworks (ZIFs) with sodalite topology, i.e. isoreticular to ZIF-8, unachievable by conventional synthetic routes, have been prepared using a solvent-free methodology. In particular, the versatility of this method is demonstrated with three different metal centres (Zn, Co and Fe) and binary combinations of three different ligands (2-methylimidazole, 2-ethylimidazole and 2-methylbenzimidazole). One combination of ligands, 2-ethylimidazole and 2-methylbenzimidazole, results in the formation of SOD frameworks for the three metal centres despite this topology not being obtained for the individual ligands. Theoretical calculations confirm that this topology is the lowest in energy upon ligand mixing

Multivariate sodalite zeolitic imidazolate frameworks: a direct solvent-free synthesis

Different mixed-ligand Zeolitic Imidazolate Frameworks (ZIFs) with sodalite topology, i.e. isoreticular to ZIF-8, unachievable by conventional synthetic routes, have been prepared using a solvent-free methodology. In particular, the versatility of this method is demonstrated with three different metal centres (Zn, Co and Fe) and binary combinations of three different ligands (2-methylimidazole, 2-ethylimidazole and 2-methylbenzimidazole). One combination of ligands, 2-ethylimidazole and 2-methylbenzimidazole, results in the formation of SOD frameworks for the three metal centres despite this topology not being obtained for the individual ligands. Theoretical calculations confirm that this topology is the lowest in energy upon ligand mixing

Electronic, Structural and Functional Versatility in Tetrathiafulvalene-Lanthanide Metal-Organic Frameworks

Tetrathiafulvalene-Lanthanide (TTF-Ln) Metal-Organic Frameworks (MOFs) are an interesting class of multifunctional materials in which porosity can be combined with electronic properties such as electrical conductivity, redox activity, luminescence and magnetism. Herein we report a new family of isostructural TTF-Ln MOFs, denoted as MUV-5(Ln) (Ln = Gd, Tb, Dy, Ho, Er), exhibiting semiconducting properties as a consequence of the short intermolecular S···S contacts established along the chain direction between partially oxidised TTF moieties. In addition, this family shows photoluminescence properties and single-molecule magnetic behaviour, finding near-infrared (NIR) photoluminescence in the Yb/Er derivative and slow relaxation of the magnetisation in the Dy and Er derivatives. As such properties are dependent on the electronic structure of the lanthanide ion, we emphasise the immense structural, electronic and functional versatility of this class of materials.</div

Defect-Free Chemical Functionalization of Magnetic Monolayers Based on Coordination Polymers

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 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